Method of manufacturing semiconductor device over glass substrate having heat resistance

ABSTRACT

When a crystalline semiconductor thin film formed by using a catalytic element for facilitating crystallization is subjected to a heat treatment in an atmosphere containing a halogen element at a temperature exceeding 700° C., a crystal structure in which crystal grain boundaries do not substantially exist can be obtained. In the present invention, the foregoing crystalline semiconductor thin film is formed on a crystallized glass substrate which is inexpensive and has high heat resistance, so that an inexpensive semiconductor device can be provided.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device using acrystalline semiconductor thin film formed on a substrate having aninsulating surface.

Incidentally, in the present specification, any of a thin filmtransistor (hereinafter referred to as a TFT), a semiconductor circuit,an electrooptical device, and an electronic equipment are included inthe category of the semiconductor device. That is, any device capable offunctioning by using semiconductor characteristics will be referred toas the semiconductor device.

Thus, the semiconductor device recited in claims of the presentapplication includes not only a single component, such as a thin filmtransistor, but also a semiconductor circuit or an electrooptical deviceformed by integrating such single components, and further, an electronicequipment having those as parts.

2. Description of the Related Art

In recent years, attention has been paid to a technique for constructinga thin film transistor (TFT) by using a semiconductor thin film (itsthickness is about several tens to several hundreds nm) formed on asubstrate having an insulating surface. With respect to the thin filmtransistor, the development thereof particularly as a switching elementfor an image display device (for example, a liquid crystal displaydevice: LCD) has been hastened.

For example, in the liquid crystal display device, trials have been madeto apply TFTs to any electric circuit, such as a pixel matrix circuitfor individually controlling pixel regions arranged in matrix, a drivingcircuit for controlling the pixel matrix circuit, and a logic circuit(calculation circuit, memory circuit, clock generator, etc.) forprocessing data signals from the outside.

In the present circumstances, although a TFT using a noncrystallinesilicon film (amorphous silicon film) as an active layer is put topractical use, a TFT using a crystalline silicon film (polysilicon filmor the like) is necessary for an electric circuit required theperformance of further high speed operation, such as a driving circuitor a logic circuit.

Conventionally, high temperature annealing has been required to form apolycrystalline silicon film having high crystallinity. Such apolycrystalline silicon film is generally referred to as hightemperature polysilicon. For the purpose of forming the high temperaturepolysilicon film, it is necessary to prepare a substrate having highheat resistance so that the substrate can withstand a processtemperature near 1000° C. For that reason, in the present circumstances,a quartz substrate (according to circumstances, a silicon substrate) isused.

However, the quartz substrate has a high unit cost, so that the quartzsubstrate has problems of increasing the cost of manufacture, andfurther, increasing the cost of a product. Thus, in recent years,attention has been paid to a low temperature polysilicon film formed onan inexpensive glass substrate, and the research of the high temperaturepolysilicon film has been gradually declined.

The coefficient of thermal expansion of the quartz substrate is about0.48×10⁻⁶° C.⁻¹, which is as small as about {fraction (1/10)} of thecoefficient of thermal expansion of silicon (about 4.15×10⁻⁶° C.⁻¹).That is, stress is apt to occur between the quartz substrate andsilicon, and peeling (film peeling) of silicon or the like is apt tooccur at a heat treatment.

Moreover, since it is difficult to make the quartz substrate large, theuse of a TFT using the high temperature polysilicon is limited to aliquid crystal display device with a size of about 1 to 2 inches indiagonal for a projection type projector or the like. That is, there isa problem that such a TFT can not be used for display devices of theseveral tens inch class, such as a display for a note-sized personalcomputer.

As a method of forming a crystalline silicon film on a glass substrate,there are known techniques disclosed in Japanese Patent UnexaminedPublication No. Hei. 7-130652 and No. Hei. 8-78329 by the same assigneeas the present application. The techniques disclosed in thesepublications use a catalytic element for facilitating crystallization ofan amorphous silicon film, so that the formation of the crystallinesilicon film having excellent crystallinity can be made by a heattreatment at about 500 to 600° C. and for about 4 hours.

Particularly, the technique disclosed in Japanese Patent UnexaminedPublication No. Hei. 8-78329 makes crystal growth almost parallel to thesubstrate surface by applying the above technique. The present inventorset al. refer to the formed crystallized region particularly as ahorizontal growth region (or lateral growth region).

However, even if a driving circuit is constructed by using such TFTs,the circuit does not still reach the state in which the requiredperformance is completely satisfied. Particularly, in the presentcircumstances, it is impossible to construct a high speed logic circuitrequiring an extremely high speed operation ranging from megahertz togigahertz by conventional TFTS.

The present inventors have repeated various processes of trial and errorto improve crystallinity of a crystalline silicon film (called apolysilicon film) including crystal grain boundaries. A semiamorphoussemiconductor (Japanese Patent Unexamined Publication No. Sho.57-160121), a monodomain semiconductor (Japanese Patent UnexaminedPublication No. Hei. 8-139019), and the like can be sited.

The common concept of semiconductor films disclosed in the abovepublications is to make the crystal grain boundaries substantiallyharmless. That is, the most important object is to substantiallyeliminate the crystal grain boundaries to cause the movement of carriers(electrons or holes) to smoothly move.

However, it can be said that even the semiconductor film disclosed inthe above publications is insufficient to carry out the high speedoperation required by a logic circuit. That is, in order to realize asystem-on-panel having a built-in logic circuit, the development of acompletely novel material is required.

SUMMARY OF THE INVENTION

The present invention has been made in order to satisfy the aboverequirements, and an object thereof is to realize a semiconductor devicehaving extremely high performance, which can construct such a high speedlogic circuit as can not be manufactured by conventional TFTs.

In order to achieve the above object, according to a first aspect of thepresent invention, a semiconductor device comprises a glass substratehaving a distortion point of not lower than 750° C., an insulatingsilicon film formed on at least a front surface and a back surface ofthe glass substrate, and a TFT including a channel formation region of asemiconductor thin film made of a collective of a plurality of rod-likeor flattened rod-like crystals and formed on the insulating siliconfilm, and the semiconductor device is characterized in that the planeorientation of the channel formation region is roughly {110}orientation, and not less than 90% of crystal lattices have continuityat crystal grin boundaries.

According to another aspect of the present invention, a semiconductordevice comprises a glass substrate having a distortion point of notlower than 750° C., an insulating silicon film formed on at least afront surface and a back surface of the glass substrate, and a TFTincluding a channel formation region of a semiconductor thin film madeof a collective of a plurality of rod-like or flattened rod-likecrystals and formed on the insulating silicon film, and thesemiconductor device is characterized in that the plane orientation ofthe channel formation region is roughly {110} orientation, and not lessthan 90% of lattice stripes observed to cross crystal grain boundariesare linearly continuous between different crystal grains forming thecrystal grain boundaries.

According to still another aspect of the present invention, asemiconductor device comprises a glass substrate having a distortionpoint of not lower than 750° C., an insulating silicon film formed on atleast a front surface and a back surface of the glass substrate, and aTFT including a channel formation region of a semiconductor thin filmmade of a collective of a plurality of rod-like or flattened rod-likecrystals and formed on the insulating silicon film, and thesemiconductor device is characterized in that an electron beamdiffraction pattern observed when the channel formation region isvertically irradiated with an electron beam has regularity peculiar to{110} orientation.

According to still another aspect of the present invention, asemiconductor device comprises a glass substrate having a distortionpoint of not lower than 750° C., an insulating silicon film formed on atleast a front surface and a back surface of the glass substrate, and aTFT including a channel formation region of a crystalline semiconductorthin film formed on the insulating silicon film.

According to still another aspect of the present invention, asemiconductor device comprises a glass substrate having a distortionpoint of not lower than 750° C., an insulating silicon film formed on atleast a front surface and a back surface of the glass substrate, and aTFT including a channel formation region of a high temperaturepolysilicon film formed on the insulating silicon film.

Still another aspect of the present invention is characterized bycomprising a glass substrate having a distortion point of not lower than750° C., an insulating silicon film formed on at least a front surfaceand a back surface of the glass substrate, and a TFT including a channelformation region of a crystalline semiconductor thin film formed on theinsulating silicon film. Yet another aspect of the present invention ischaracterized by comprising a glass substrate having a distortion pointof not lower than 750° C., an insulating silicon film formed on at leasta front surface and a back surface of the glass substrate, and a TFTincluding a channel formation region of a high temperature polysiliconfilm formed on the insulating silicon film.

The following three points can be enumerated as the important structuralconditions of the present invention.

(1) A glass substrate (glass substrate having a distortion point of notlower than 750° C.) having such heat resistance that the substrate canwithstand the temperature of not lower than 750° C. is used as asubstrate.

(2) The outer surface (at least the front surface and the back surface,preferably all surfaces) of the high heat-resistant glass substrate isprotected with an insulating silicon film.

(3) A crystalline semiconductor thin film excellent in conformity ofcrystal grain boundary is provided on the high heat-resistant glasssubstrate covered with the insulating silicon film.

In order to form the crystalline semiconductor thin film excellent inthe conformity of crystal grain boundary developed by the presentinventors, a heat treatment at a temperature exceeding 700° C. isrequired. The details of this forming method will be described in thesection of “Detailed Description of the Invention”.

For the above reason, it is necessary to use a substrate having adistortion point of not lower than 750° C. As such a substrate, althougha quartz substrate is common, since the quartz substrate is expensive,the total cost is increased. Moreover, the coefficient of thermalexpansion is 0.48×10⁻⁶° C.⁻¹, and is as small as about {fraction (1/10)}of the coefficient of thermal expansion of silicon (about 4.15×10⁻⁶°C.⁻¹). That is, stress is apt to occur between the quartz substrate andsilicon, and peeling (film peeling) of silicon or the like is apt tooccur at heat treatment.

Then, in the present invention, a crystallized glass having a distortionpoint of not lower than 750° C. (typically 950 to 1100° C., preferably1000 to 1050° C.) and having high heat resistance is used as asubstrate. Since the crystallized glass can be made thinner than quartz,the cost of manufacture of a liquid crystal module or the like can bekept inexpensive. Moreover, because of the glass substrate, it ispossible to make the substrate large, and it is also possible to designa reduction in costs by formation of plural products from one substrateaccording to multiple-face taking.

Further, the coefficient of thermal expansion can be easily changed byadjusting the constituents of the crystallized glass. Thus, it is easyto select the coefficient of thermal expansion near the coefficient ofthermal expansion of the crystalline semiconductor thin film.

The present inventors aim at obtaining a system-on-panel, and realizingan inexpensive and high performance electronic equipment. For thepurpose of actively using the merits, it is greatly more effective touse the inexpensive crystallized glass than the expensive quartzsubstrate.

However, since the crystallized glass has various constituents, there isa fear of outflow of constituents in the manufacturing steps of asemiconductor device. Thus, it is important to protect the crystallizedglass with an insulating film (an insulating silicon film is preferablein view of affinity to a crystalline silicon film). For that purpose, inthe entire process, it is necessary to protect at least the frontsurface and the back surface of the crystallized glass with theinsulating film.

Since the side surface of the crystallized glass has a very small areaon the whole, even if the side surface is exposed, a serious problemdoes not occur. However, it is needless to say that it is mostpreferable to completely cover the front surface, the side surface, andthe back surface with the insulating film to completely prevent theoutflow of the constituents.

However, a portion on which the insulating film is not formed occurs ata substrate supporting portion (pusher pin and the like) used in thefilm formation of the insulating film. However, since this portion isvery small as compared with the total area, a problem does not occur.

In view of the above, the present inventors have reached the structureof the present invention that a crystalline semiconductor thin filmexcellent in conformity at crystal grain boundaries is provided on ahigh heat-resistant glass substrate in which the outer circumferentialsurface (preferably all surfaces) of the substrate is protected with aninsulating silicon film.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIGS. 1A to 1D are views showing manufacturing steps of a semiconductorthin film;

FIGS. 2A to 2E are views showing manufacturing steps of a semiconductorthin film;

FIGS. 3A and 3B are views showing electron beam diffraction patterns;

FIGS. 4A to 4D are view showing manufacturing steps of a thin filmtransistor;

FIGS. 5A to 5C are views showing manufacturing steps of a thin filmtransistor;

FIGS. 6A to 6D are views showing manufacturing steps of a thin filmtransistor;

FIGS. 7A to 7C are views showing manufacturing steps of a thin filmtransistor;

FIG. 8 is a view showing the structure of a thin film transistor;

FIG. 9 is a view showing the structure of a thin film transistor;

FIG. 10 is a view showing the structure of a thin film transistor;

FIGS. 11A to 11C are views showing manufacturing steps of a thin filmtransistor;

FIGS. 12A and 12B are views showing an upper surface and a sectionalstructure of a pixel TFT;

FIG. 13 is a view showing a structure of a liquid crystal module;

FIGS. 14A and 14B are views showing the structure of a liquid crystalmodule, respectively;

FIGS. 15A to 15F are views showing the structure of an electronicequipment, respectively;

FIG. 16A is a TEM photographs showing lattice stripes of crystal grainsof a CGS film;

FIG. 16B is a TEM photographs showing lattice stripes of crystal grainsof a high temperature polysilicon film;

FIG. 17 is a view showing the result of X-ray diffraction of a CGS film;

FIGS. 18A and 18B are TEM photographs showing the state of defects ingrains of a CGS film, respectively;

FIGS. 19A to 19C are views for explaining a model relating to generationand disappearance of defects; and

FIGS. 20A and 20B are TEM photographs showing a dark field image of aCGS film, respectively.

DETAILED DESCRIPTION OF THE INVENTION

Preferred embodiments of the present invention will now be describedwith reference to the drawings.

First, steps up to the formation of a high temperature polysilicon filmwill be described with reference to FIGS. 1A to 1D. As a substrate, acrystallized glass 101 with a thickness of 0.5 to 1.1 mm (typically 0.7mm) is prepared. The crystallized glass is aIso called glass ceramics,and is defined as a glass substrate obtained by uniformly growing finecrystals at the stage of glass formation. Such crystallized glass hasfeatures that the heat resistance is high and the coefficient of thermalexpansion is small.

The glass substrate used in the present invention is required to have adistortion point of not less than 750° C., preferably 950 to 1100° C.,that is, the high heat resistance is required. In the presentcircumstances, although there is only crystallized glass as glassmaterials which realize such heat resistance, even if a glass substrate(for example, a high heat-resistant glass substrate in an amorphousstate or the like) is not included in the definition of the crystallizedglass, if the substrate has the foregoing heat resistance, the substratecan be used in the present invention.

The details of the crystallized glass may be referred to “GlassHandbook; Sumio Sakubana, et al., pp. 197 to 217, Asakura Shoten, 1975”.

Although there are various kinds of crystallized glass, basically, itcan be said that aluminosilicate glass mainly containing quartz (SiO₂)and alumina (Al₂O₃), borosilicate glass (containing B₂O₃), or the likeis practical. However, in view of the use as a substrate for asemiconductor device, non-alkaline glass is preferable. In such a sense,it is preferable to use glass of MgO—Al₂O₃—SiO₂, PbO—ZnO—B₂O₃,Al₂O₃—B₂O₃—SiO₂, ZnO—B₂O₃—SiO₂, or the like.

The high insulation crystallized glass of MgO—Al₂O₃—SiO₂ includes TiO₂,SnO₂, ZrO₂ or the like as a nucleus formation agent, and is crystallizedglass having cordierite (2 MgO2Al₂O₃5SiO₂) as a main crystal phase. Thistype of crystallized glass has features that the heat resistance is highand the electric insulation is superior even in the range of highfrequency. An example of the constituents and the coefficient of thermalexpansion of cordierite-based crystallized glass is shown in Table 1.

TABLE 1 Coefficient of Constituent of glass (wt %) thermal expansion ×SiO₂ Al₂O₃ Mgo TiO₂ 10⁻⁶ (° C.)⁻¹ 40-60 20-30 13-14 9-13 1.5-6.5

As the coefficient of thermal expansion becomes small, an influence ofshrinkage due to heat becomes small. Thus, a substrate having a smallcoefficient of thermal expansion is preferable as a substrate forsemiconductor in which minute pattern working is carried out. However,if the difference from the coefficient of thermal expansion of asemiconductor thin film is large, peeling or the like becomes apt tooccur. Thus, it is preferable to use a substrate having a coefficient ofthermal expansion near the coefficient of thermal expansion of asemiconductor thin film to the utmost degree. In view of these, it canbe said that the cordierite-based crystallized glass containing SiO₂ of45 to 57%, Al₂O₃ of 20 to 27%, MgO of 11 to 18%, and TiO₂ of 9 to 12% ispreferable.

In the case where a transmission type LCD is manufactured, transparencyis required for crystallized glass. In such a case, it is appropriatethat non-alkaline transparent crystallized glass is used. For example,there is crystallized glass as shown in Table 2 as crystallized glass inwhich the crystal phase is filled β-quartz solid solution and thecoefficient of thermal expansion is 1.1 to 3.0×10⁻⁶° C.

TABLE 2 Coefficient of Constituent of glass (wt %) thermal expansion ×SiO₂ Al₂O₃ MgO ZnO ZrO₂ 10⁻⁶ (° C.)⁻¹ 64-75 16-25 3-10 0-7 3-10 1.1-3.0

The first structural conditions of the present invention is to use suchcrystallized glass as a substrate. Of course, if suitable contrivance(for example, completely protecting a substrate with an insulating filmas in the present invention) is made, alkaline crystallized glass(Na₂O—Al₂O₃—SiO₂, Li₂O—Al₂O₃—SiO₂, or the like) may be used. Even if thecoefficient of thermal expansion of the crystallized glass is very small(near zero), it is also possible to relax the difference in thecoefficient of thermal expansion from a semiconductor thin film bycoating the crystallized glass with glass having a coefficient ofthermal expansion of 2.0 to 3.0×10⁻⁶° C.

After the crystallized glass 101 having the above described structure isprepared, an amorphous silicon film 102 is formed on the crystallizedglass 101. The film formation is carried out by a low pressure CVDmethod, and silane (SiH₄) or disilane (Si₂H₆) is used as a filmformation gas. It is appropriate that the thickness is made 50 to 250 nm(typically 100 to 150 nm) (FIG. 1(A)).

When the film is formed by the low pressure CVD method in this way, itis possible to form the amorphous silicon film 102 on the front surface,the back surface, and the side surface so as to cover the crystallizedglass 101. Strictly speaking, the amorphous silicon film 102 is notformed at a portion with which a pusher pin for supporting the substrateis brought into contact. However, the portion is very small as comparedwith the total area.

Next, a heat treatment is carried out to completely thermally oxidizethe amorphous silicon film 102 to form a thermal oxidation film 103. Inthis case, since the amorphous silicon film 102 is completely thermallyoxidized and is changed into the thermal oxidation film 103, thethickness of the thermal oxidation film 103 becomes 100 to 500 nm(typically 200 to 300 nm).

The condition of the heat treatment may be any means of well known dryO₂ oxidation, wet O₂ oxidation, steam oxidation, pyrogenic oxidation,oxygen partial pressure oxidation, and hydrochloric acid (HCl)oxidation. It is appropriate that suitable conditions are set for theprocess temperature and the process time in view of the process.

The heat treatment is carried out at a temperature not less than thedistortion point of the crystallized glass and not higher than a gradualcooling point, and it is preferable to carry out such a process thatafter the temperature is kept, process temperature is gradually lowered.When such a process is carried out, countermeasures against shrinkage ofglass can be taken at the same time as the formation of the thermaloxidation film. That is, when the substrate is sufficiently shrunken bythe above process, it is possible to lower the amount of shrinkage ofthe substrate due to a subsequent heat treatment. The technique relatingto this is disclosed in Japanese Patent Unexamined Publication No. Hei.8-250744.

In the manner as described above, although the thermal oxidation film(silicon oxide film) 103 is formed, as described above, the amorphoussilicon film 102 is formed so as to cover the crystallized glass 101, sothat the thermal oxidation film 103 is also formed so as to cover thecrystallized glass 101. That is, since the crystallized glass 101 iscompletely covered with the insulating silicon film, it becomes possibleto prevent the outflow of constituents.

Here, although the silicon oxide film expressed by SixOy is used as theinsulating silicon film, other insulating silicon films, such as asilicon nitride film expressed by SixNy or a silicon nitride oxide filmexpressed by SiOxNy, may be used.

In this way, two of the important conditions of the present invention,that is, using crystallized glass and covering the crystallized glasswith an insulating silicon film can be achieved.

Next, a technique for forming a high temperature polysilicon film willbe described. After the state shown in FIG. 1B is obtained, an amorphoussilicon film 104 is formed by a low pressure CVD method, a plasma CVDmethod, or a sputtering method (FIG. 1C).

It is also possible to use a compound of silicon and germanium expressedby Si_(X)Ge_(1−X) (0<X<1) instead of the amorphous silicon film 104. Thethickness of the amorphous silicon film 104 is made 25 to 150 nm(preferably 50 to 100 nm).

Since there is a possibility that impurities, such as carbon, oxygen,and nitrogen, mixed during the film formation hinder subsequentcrystallization, it is preferable to thoroughly lower them.Specifically, it is preferable to make management so that theconcentration of each of carbon and nitrogen is less than 5×10¹⁸atoms/cm³ (typically 5×10¹⁷ atoms/cm³ or less), and the concentration ofoxygen is less than 1.5×10¹⁹ atoms/cm³ (typically 1×10¹⁸ atoms/cm³ orless). If the concentration of the impurities is made the foregoingvalue at the film formation, the concentration of the impurities in acompleted TFT is also restricted within the foregoing range.

It is effective to add an impurity element (an element in group 13,typically boron, or an element in group 15, typically phosphorus) forcontrolling the threshold voltage (Vth) of the TFT at the filmformation. The amount of addition must be determined in view of vth inthe case where the foregoing Vth controlling impurity element is notadded.

Next, a crystallizing step of the amorphous silicon film 104 is carriedout. This step is carried out by furnace annealing after the amorphoussilicon film 104 is cleaned. Specifically, a heat treatment at 600° C.for 24 hours is carried out in an electric heating furnace of an inertgas atmosphere (typically, nitrogen atmosphere) to make crystallizationdue to generation of natural nuclei. As the need arises, an oxygenannealing step or a nitrogen annealing step at a temperature of 700 to900° C. may be added after the crystallization. In this way, thecrystallization is made, so that a high temperature polysilicon film 105is obtained (FIG. 1D).

The thus formed high temperature polysilicon film 105 is structured suchthat needle-like crystals are irregularly collected. The orientation isalso irregular, and the orientation ratios of {111} plane and {110}plane are 0.6 or less, and the main orientation plane does not exist.This is also found from the fact that diffraction spots seen in theelectron diffraction pattern are irregular. Incidentally, theorientation ratio is obtained from the definition disclosed in JapanesePatent Unexamined Publication No. Hei. 7-321339 by the present inventorset al.

Since the high temperature polysilicon film 105 is formed through theheat treatment at a temperature exceeding at least 800° C., the densityof defects in crystal grains is very low. That is, the spin densitymeasured by an ESR method is very small.

It is certain that the high temperature silicon film shows the spindensity lower than at least other polysilicon films formed within atemperature range not larger than 800° C. (including a film using lasercrystallization as well). Thus, the electric characteristics of a TFTusing the high temperature polysilicon film are excellent.

Although an object of the present invention is to manufacture asemiconductor device using a high temperature polysilicon film at lowcost, it is needless to say that the semiconductor thin film formed onthe crystallized glass is not limited to only the high temperaturepolysilicon film.

The most important structure of the present invention is to protect atleast the front surface and the back surface (preferably all surfaces)of crystallized glass with an insulating silicon film, and asemiconductor thin film formed thereon may be any semiconductor thinfilm as long as the process temperature is restricted within thetemperature range not higher than the distortion point of thecrystallized glass.

Next, steps to the point when a crystalline semiconductor thin film moreexcellent in the conformity of crystal grain boundary than the hightemperature polysilicon film is formed, will be described with referenceto FIGS. 2A to 2E. First, a crystallized glass 101 with a thickness of0.5 to 1.1 mm (typically 0.7 mm) is prepared as a substrate. Thecrystallized glass to be used has been described in the explanation offormation of the high temperature polysilicon film.

After the crystallized glass 101 having the above described structure isprepared, an amorphous silicon film 202 is formed on the crystallizedglass 101. The film formation is carried out by a low pressure CVDmethod, and silane (SiH₄) or disilane (Si₂H₆) is used as a film forminggas. It is appropriate that the thickness is made 50 to 250 nm(typically 100 to 150 nm) (FIG. 2A).

When the film is formed by the low pressure CVD method in this way, itis possible to form the amorphous silicon film 202 on the front surface,the back surface and the side surface so as to cover the crystallizedglass 101. Strictly speaking, the amorphous silicon film 202 is notformed at a portion with which a pressure pin for supporting thesubstrate is brought into contact. However, the portion is very small ascompared with the total area.

Next, a heat treatment is carried out to completely thermally oxidizethe amorphous silicon film 202 so that a thermal oxidation film 203 isformed. In this case, since the amorphous silicon film 202 is completelythermally oxidized and is changed into the thermal oxidation film 203,the thickness of the thermal oxidation film 203 becomes 100 to 500 nm(typically 200 to 300 nm).

The condition of the heat treatment may be any means of well known dryO₂ oxidation, wet O₂ oxidation, steam oxidation, pyrogenic oxidation,oxygen partial pressure oxidation, and hydrochloric acid oxidation(HCl). It is appropriate that suitable conditions are set for theprocess temperature and the process time in view of the process.

The heat treatment is carried out at a temperature not less than thedistortion point of the crystallized glass and not higher than a gradualcooling point, and it is preferable to carry out such a process thatafter the temperature is kept, process temperature is gradually lowered.When such a process is carried out, countermeasures against shrinkage ofglass can be taken at the same time as the formation of the thermaloxidation film. That is, when the substrate is sufficiently shrunken bythe above process, it is possible to lower the amount of shrinkage ofthe substrate due to a subsequent heat treatment. The technique relatingto this is disclosed in Japanese Patent Unexamined Publication No. Hei.8-250744.

In the manner as described above, although the thermal oxidation film(silicon oxide film) 203 is formed, the amorphous silicon film 202 isformed so as to cover the crystallized glass 101 as described above, sothat the thermal oxidation film 203 is also formed so as to cover thecrystallized glass 101. That is, since the crystallized glass 101 iscompletely covered with the insulating silicon film, it becomes possibleto prevent the outflow of constituents.

Here, although the silicon oxide film expressed by SixOy is used as theinsulating silicon film, other insulating silicon films, such as asilicon nitride film expressed by SixNy or a silicon nitride oxide filmexpressed by SiOxNy, may be used.

In this way, two of the important conditions of the present invention,that is, using crystallized glass and covering the crystallized glasswith an insulating silicon film can be achieved.

Next, a technique for forming a crystalline semiconductor thin filmexcellent in the conformity of crystal grain boundary will be described.After the state shown in FIG. 2B is obtained, an amorphous semiconductorthin film 204 is formed by a low pressure CVD method, a plasma CVDmethod, or a sputtering method.

However, in the case where the film is formed by the low pressure CVDmethod, it is preferable to remove the film formed on the back surfaceand the side surface before a subsequent crystallizing step is carriedout. According to the experiences of the present inventors, it appearsthat the crystal state is degraded if the crystallizing step is carriedout while the amorphous semiconductor thin film remains at the backsurface and the side surface (the cause is not known).

As the amorphous semiconductor thin film 204, it is appropriate totypically use an amorphous silicon film. As other semiconductor thinfilms, it is also possible to use a compound of silicon and germaniumexpressed by Si_(X)Ge_(1−X) (0<X<1). The thickness of the amorphoussilicon film 204 is made 25 to 100 nm (preferably 30 to 60 nm).

Since there is a possibility that impurities, such as carbon, oxygen,and nitrogen, mixed during the film formation hinder subsequentcrystallization, it is preferable to thoroughly reduce them.Specifically, it is preferable to make management so that theconcentration of each of carbon and nitrogen is less than 5×10¹⁸atoms/cm³ (typically 5×10¹⁷ atoms/cm³ or less), and the concentration ofoxygen is less than 1.5×10¹⁹ atoms/cm³ (typically 1 ×10¹⁸ atoms/cm³ orless). If the concentration of the impurities is made the foregoingvalue at the film formation, the concentration of the impurities in acompleted TFT is also restricted within the foregoing range.

It is effective to add an impurity element (an element in group 13,typically boron, or an element in group 15, typically phosphorus) forcontrolling the threshold voltage (Vth) of a TFT at the film formation.The amount of addition must be determined in view of Vth in the casewhere the foregoing Vth controlling impurity element is not added.

Next, a crystallizing step of the amorphous semiconductor thin film 204is carried out. As a means for crystallization, a technique disclosed inJapanese Patent Unexamined Publication No. Hei. 7-130652 by the presentinventors et al. is used. Any means of Embodiment 1 and Embodiment 2 ofthe publication may be used, in the present invention, it is preferableto use the technical contents (described in Japanese Patent UnexaminedPublication No. Hei. 8-78329 in detail) set forth in Embodiment 2.

According to the technique disclosed in Japanese Patent UnexaminedPublication No. Hei. 8-78329, a mask insulating film 205 for selectingan added region of a catalytic element is first formed. Then a solutioncontaining a catalytic element for facilitating the crystallization ofthe amorphous semiconductor thin film 204 is applied by a spin coatingmethod to form a catalytic element containing layer 206 (FIG. 2C).

As the catalytic element, one kind of or plural kinds of elementsselected from nickel (Ni), cobalt (Co), iron (Fe), palladium (Pd),platinum (Pt), copper (Cu), gold (Au), Germanium (Ge), and lead (Pb) maybe used. Especially, it is preferable to use nickel excellent inconformity of lattices to silicon.

The adding step of the foregoing catalytic element is not limited to thespin coating method, but an ion implantation method or a plasma dopingmethod using a mask may also be used. In this case, since it becomeseasy to decrease an occupied area of an added region and to control agrowth distance of a lateral growth region, the method becomes aneffective technique when a minute circuit is formed.

Next, after the adding step of the catalytic element is ended,dehydrogenating is carried out at about 500° C. for 2 hours, and then aheat treatment is carried out in an inert gas atmosphere, a hydrogenatmosphere, or an oxygen atmosphere at a temperature of 500 to 700° C.(typically 550 to 650° C., preferably 570° C.) for 4 to 24 hours tocrystallize the amorphous semiconductor thin film 204 (FIG. 2D).

At this time, the crystallization of the amorphous semiconductor thinfilm 204 progresses first from nuclei generated in a region added withnickel, and a crystal region 207 grown almost parallel to the substratesurface of the crystallized glass 101 is formed. The present inventorsrefer to this crystal region 207 as a lateral growth region. Sincerespective crystals in the lateral growth region are gathered in acomparatively uniform state, the lateral growth region has such anadvantage that the total crystallinity is superior (FIG. 2D).

After the heat treatment for crystallization is ended, the maskinsulating film 205 is removed, and then, a heat treatment (getteringprocess for the catalytic element) for removing the catalytic element iscarried out. In this heat treatment, a halogen element is made containedin a processing atmosphere and the gettering effect for a metallicelement by the halogen element is used.

In order to sufficiently obtain the gettering effect by the halogenelement, it is preferable to carry out the above heat treatment at atemperature exceeding 700° C. If the temperature is not higher than 700°C., it becomes difficult to decompose a halogen compound in theprocessing atmosphere, so that there is a fear that the gettering effectcan not be obtained. Thus, the heat treatment is carried out preferablyat a temperature of 800 to 1000° C. (typically 950° C.), and aprocessing time is made 0.1 to 6 hours, typically 0.5 to 1 hour.

As a typical example, it is appropriate that a heat treatment is carriedout in an oxygen atmosphere containing hydrogen chlorine (HCl) of 0.5 to10 vol% (preferably, 3 vol%) at 950° C. for 30 minutes. If theconcentration of HCl is higher than the above-mentioned concentration,asperities comparable to a film thickness are produced on the surface ofthe lateral region 207. Thus, such a high concentration is notpreferable.

As a compound containing a halogen element, one kind or plural kinds ofcompounds selected from compounds containing halogen elements, such asHF, NF₃, HBr, Cl₂, ClF₃, BCl₃, F₂, and Br₂, may be used other than theHCl gas.

In this step, the catalytic element in the lateral growth region 207 isgettered by the action of chlorine and is transformed into volatilechloride which is released into the air. After this gettering step, theconcentration of the catalytic element in the lateral growth region 208is lowered down to 5×10¹⁷ atoms/cm³ or less (typically 2×10¹⁷ atoms/cm³or less).

The thus obtained lateral growth region 208 shows a unique crystalstructure made of a collective of rod-like or flattened rod-likecrystals. Its features will be described below.

Findings as to Crystal Structure of an Active Layer

An active layer of a TFT using the lateral growth region formed inaccordance with the foregoing manufacturing steps has microscopically acrystal structure in which a plurality of rod-like (or flattenedrod-like) crystals are arranged in almost parallel to each other andwith regularity to a specific direction. This can be easily ascertainedby observation with a TEM (Transmission Electron Microscope).

FIGS. 16A and 16B are HR-TEM photographs showing crystal grainboundaries of rod-like or flattened rod-like crystals, magnified eightmillion times. In the present specification, the crystal grain boundaryis defined as a grain boundary formed at an interface where rod-like orflattened rod-like crystals are in contact with each other. Thus, thecrystal grain boundary is regarded as different from, for example, amacroscopic grain boundary formedby collision of lateral growth regions.

Incidentally, the foregoing HR-TEM (High Resolution TransmissionElectron Microscope) is a method in which a sample is verticallyirradiated with an electron beam, and the arrangement of atoms andmolecules is estimated by using interference of transmitted electrons orelastically scattered electrons.

In the HR-TEM, it is possible to observe the state of arrangement ofcrystal lattices as lattice stripes. Thus, by observing the crystalgrain boundary, it is possible to infer the bonding state of atoms inthe crystal grain boundary. Incidentally, although lattice stripesappear as stripe patterns of black and white, they show the differencein contrast, and do not show the position of atoms.

FIG. 16A is a typical TEM photograph of a crystalline silicon filmobtained by the present invention, and the state where two differentcrystal grains are in contact with each other at the crystal grainboundary seen from the upper left to the lower right in the photographis observed. At this time, the two crystal grains were almost in {110}orientation although some deviations were included in crystal axes.

Although described later, as the result of investigation of a pluralityof crystal grains, it is ascertained by X-ray diffraction and electronbeam diffraction that almost all crystal grains are substantially in the{110} orientation. Although many observed crystal grains ought toinclude a (001) plane, (200) plane, and the like, those equivalentplanes will be expressed together by a {110} plane.

As shown in FIG. 16A, lattice stripes corresponding to a {111} plane and{100} plane are observed in a face. Incidentally, the lattice stripecorresponding to the {111} plane indicates such a lattice stripe thatwhen a crystal grain is cut along the lattice stripe, the {111} planeappears in the section. In a simplified manner, it is possible toascertain by the distance between the lattice stripes to what plane thelattice stripe corresponds.

The reason why there is a difference in the appearance of the latticestripes in FIG. 16A is that the slopes of the crystal grains are subtlydifferent. That is, when it is designed so that the crystal face of oneof crystal grains is vertically irradiated with an electron beam, theother crystal grain is slightly obliquely irradiated with the electronbeam. Thus, the appearance of the lattice stripe is changed.

Here, attention is paid to the lattice stripe corresponding to the {111}plane. In FIG. 16A, the lattice stripe corresponding to the {111} planeof the crystal grain at the upper side above the grain boundaryintersects the lattice stripe corresponding to the {111} plane of thecrystal grain at the lower side at an angle of about 70° (precisely70.5°).

Such crystal structure (precisely, the structure of crystal grainboundary) shows that two different crystal grains are in contact witheach other with extremely excellent conformity. That is, the crystallattices are continuous at the crystal grain boundary so that they makesuch a structure that it is very hard to produce trap levels due tocrystal defects and the like. In other words, it can be said that thecrystal lattices have continuity at the crystal grain boundary.

For reference, FIG. 16B shows an HR-TEM photograph of a conventionalhigh temperature poolysilicon film. In the case of FIG. 16B, althoughdescribed later, there was no regularity in the crystal plane, and theorientation was not such that the {110} plane became main. However, forcomparison to FIG. 16A, observation was made here to such crystal grainsthat the lattice stripe corresponding to the {111} plane appeared.

When FIG. 16B is observed in detail, as shown by an arrow in thedrawing, many portions where the lattice stripes are disconnected can beascertained in the crystal grain boundary. In such portions, there areuncombined bonds (which can be called crystal defects), and there is ahigh possibility that as trap levels, they block the movement ofcarriers.

However, it is certain that the semiconductor thin film of the presentinvention also includes uncombined bonds as shown in FIG. 16B. This isinevitable as long as the semiconductor thin film of the presentinvention is polycrystal. However, as the result of TEM observation indetail for the semiconductor thin films of the present invention over awide range, it has been found that such uncombined bonds are very few.

The present inventors refer to the bonding state of atoms in the casewhere the lattice strips correspond to each other with excellentconformity, like the semiconductor thin film used in the presentinvention, as conformity bond, and refer to chemical bonds at that timeas conformity chemical bonds. On the contrary, the present inventorsrefer to the bonding state of atoms in the case where the latticestripes do not correspond to each other with excellent conformity, whichis often seen in a conventional high temperature polysilicon film, asunconformity bond, and refer to chemical bonds at that time asunconformity chemical bonds (or unpaired bonds or uncombined bonds).

Since the semiconductor thin film used in the present invention is veryexcellent in conformity at the crystal grain boundary, the foregoingunconformity chemical bonds are very few. According to the investigationby the present inventors, the existence ratio of the unconformitychemical bonds to the total chemical bonds is 10% or less (preferably 5%or less, more preferably 3% or less). That is, 90% or more of the wholechemical bonds (preferably 95% or more, more preferably 97% or more) aremade of the conformity chemical bonds.

Also from this fact, it can be said that the crystalline silicon film ofthe present invention is a semiconductor film obviously different from aconventional high temperature polysilicon.

FIG. 3A shows the result of investigation of the semiconductor thin filmof the present invention by an electron beam diffraction. For reference,FIG. 3B shows an electron beam diffraction pattern of a conventionalhigh temperature polysilicon film. In FIGS. 3A and 3B, the diameters ofirradiation areas of the electron beams are 4.35 μm and 1.35 μm,respectively. In this embodiment, typical photographs among measurementsof plural positions are shown.

In the case of FIG. 3A, diffraction spots (diffraction fleck)corresponding to<110> incidence appear comparatively clearly, and it isascertained that almost all crystal grains are in {111} orientationwithin the irradiation area of the electron beam.

The present inventors performed X-ray diffraction in accordance with amethod disclosed in Japanese Patent Unexamined Publication No. Hei.7-321339, and calculated the ratio of orientation with respect to thesemiconductor thin film of the present invention. In the publication,the ratio of orientation is defined with the calculation method asindicated by the following expression 1:

{220} orientation existence ratio=1 (constant),

{111} orientation existence ratio=(relative strength of {111} to {220}of a sample)/(relative strength of {111} to {220} of powder),

{311} orientation existence ratio=(relative strength of {311} to {220}of a sample)/(relative strength of {311} to {220} of powder), and

{220} orientation ratio=({220} orientation existence ratio)/({220}orientation existence ratio+{111} orientation existence ratio+{311}orientation existence ratio).

As the result of investigation of the orientation of the semiconductorthin film of the present invention by the X-ray diffraction, a peakcorresponding to a (220) plane appears in the X-ray diffraction pattern.The result is shown in FIG. 17. Of course, it is needless to say thatthe (220) plane is equivalent to the {110} plane. As the result of thismeasurement, it was found that the {110} plane is the main orientedplane, and the ratio of orientation is 0.7 or more (typically 0.9 ormore).

On the other hand, in the case of the conventional high temperaturepolysilicon film shown in FIG. 3B, it was found that definite regularitycould not be seen in the diffraction spots, and they were orientedalmost at random, in other words, crystal grains with plane orientationother than the {110} plane were irregularly mixed.

Although the respective diffraction spots have small concentricexpanses, it is presumed that this is caused from a distribution ofrotation angles of some degree around a crystal axis. That is, althougha completely circular diffraction spot ought to be obtained for single,crystal, since the semiconductor thin film used in the present inventionis polycrystal, the fluctuation of the diffraction spot arises.

However, that the diffraction spot is nearly a circle means thatrotation angles existing among a plurality of crystal grains are verysmall. Thus, the semiconductor thin film of the present invention inwhich the diffraction spot is almost a circle is substantially noneother than single crystal.

As described above, the semiconductor thin film manufactured through themanufacturing steps shown in FIGS. 2A to 2E is a semiconductor thin filmhaving a crystal structure (precisely, a structure of crystal grainboundary) quite different from a conventional semiconductor thin film.The present applicant refers to the semiconductor thin film having sucha crystal structure as continuous grain boundary crystal silicon(Continuous Grain Silicon: CGS). Thus, the active layer of the TFT usedin the present invention is formed of the CGS film having such a uniquecrystal structure.

Incidentally, in the formation of the CGS film, the annealing step(here, the step shown in FIG. 2E) at a temperature above a crystallizingtemperature required for crystallization plays an important role withrespect to lowering of defects in a crystal grain. This will bedescribed.

FIG. 18A is a TEM photograph of a crystalline silicon film at the pointof time when steps up to the crystallizing step shown in FIG. 2C havebeen ended, which is magnified 250 thousands times. Zigzag defects asindicated by arrows are ascertained in the crystal grain (black portionand white portion appear due to difference of contrast).

Although such defects are mainly a lamination defect in which the orderof lamination of atoms on a silicon crystal lattice plane is discrepant,there is also a case of dislocation or the like. It appears that FIG.18A shows the lamination defect having a defect plane parallel to the{111} plane. This can be inferred from the fact that the zigzag defectsare bent at about 70°.

On the other hand, as shown in FIG. 18B, in the crystalline silicon filmof the present invention, which is magnified at the same magnification,it is ascertained that there are hardly seen defects caused by thelamination defect, dislocation, or the like, and the crystallinity isvery high. This tendency can be seen in the entire of the film surface,and although it is difficult to reduce the number of defects to zero inthe present circumstances, it is possible to reduce the number tosubstantially zero.

That is, in the crystalline silicon film shown in FIG. 18B, defects inthe crystal grain are reduced to the degree that the defects can bealmost neglected, and the crystal grain boundary can not become abarrier against the movement of carriers because of the high continuity,so that the film can be regarded as single crystal or substantiallysingle crystal.

As described above, in the crystal silicon films shown in thephotographs of FIGS. 18A and 18B, although the crystal grain boundarieshave almost equal continuity, there is a large difference in the numberof defects in the crystal grains. The reason why the crystal siliconfilm according to the present invention shows electrical characteristicsmuch higher than the crystal silicon film shown in FIG. 18A is mainlythe difference in the number of defects.

The present inventors consider the following model for a phenomenonoccurring in the step shown in FIG. 2E. First, in the state shown inFIG. 18A, the catalytic element (typically nickel) is segregated at the,defects (mainly the lamination defects) in the crystal grain. That is,it is conceivable that there are many bonds having a form such asSi—Ni—Si.

However, when Ni existing in the defects is removed by carrying out thegettering process of the catalytic element, the bond of Si—Ni is cut.Thus, the remaining bond of silicon immediately forms Si Si bond andbecomes stable. In this way, the defects disappear.

Of course, although it is known that the defects in a crystal siliconfilm disappear by thermal annealing at a high temperature, it ispresumed that in the present invention, since bonds with nickel are cutand many uncombined bonds are generated, the recombination of silicon isfurther smoothly carried out.

Moreover, at the same time, it is conceivable that surplus silicon atomsgenerated at the thermal oxidation of the crystalline silicon film moveto the defects and greatly contribute to the generation of Si—Si bond.This concept is known as the reason why defects are few in the so-calledhigh temperature polysilicon film.

Besides, the present inventors consider a model in which the crystallinesilicon film is bonded to its under film by a heat treatment at atemperature (typically, 700 to 1100° C.) above the crystallizingtemperature and adhesiveness is increased, so that the defectsdisappear.

There is a difference of nearly 10 times in thermal expansioncoefficient between the crystal silicon film and the silicon oxide filmas the under film. Thus, in the state (FIG. 18A) in which the amorphoussilicon film is transformed into the crystal silicon film, a very largestress is applied to the crystal silicon film when the crystal siliconfilm is cooled.

This will be described, with reference to FIGS. 19A to 19C. FIG. 19Ashows heat hysteresis applied to the crystal silicon film after thecrystallizing step. First, the crystal silicon film crystallized at atemperature (t₁) is cooled to room temperature through a cooling period(a).

FIG. 19B shows the crystal silicon film during the cooling period (a),in which reference numeral 10 denotes a quartz substrate, and 11 denotesa crystal silicon film. At this time, adhesiveness at an interface 12between the crystal silicon film 11 and the substrate 10 is not veryhigh, and it is conceivable that this causes production of many defectsin grains.

That is, it is conceivable that the crystal silicon film 11 pulled dueto the difference in the coefficient of thermal expansion is very easilymoved on the quartz substrate 10, so that defects 13 such as laminationdefects or dislocations are easily produced by force such as tensilestress.

The thus obtained crystal silicon film becomes the state as shown inFIG. 18A. Thereafter, as shown in FIG. 19A, the gettering step of thecatalytic element is carried out at a temperature (t₂), and as theresult, the defects in the crystal silicon film disappear because of theabove-described reason.

The important point here is that the crystal silicon film is bonded tothe quartz substrate at the same time as the gettering step of thecatalytic element, so that the adhesiveness to the quartz substrate israised. That is, it is conceivable that this gettering step also servesas a bonding step of the crystal silicon film to the quartz substrate(under film).

After the gettering+bonding step is ended in this way, the film iscooled to room temperature through a cooling period (b). Here, thedifferent point from the cooling period (a) after the crystallizing stepis that an interface 15 between the quartz substrate 10 and a crystalsilicon film 14 after annealing is in a state having very highadhesiveness (FIG. 19C).

When the adhesiveness is high like this, since the crystal silicon film14 is completely bonded to the quartz substrate 10, even if stress isapplied to the crystal silicon film at the cooling stage of the crystalsilicon film, defects are not produced. That is, it is possible toprevent defects from being produced again.

Incidentally, in FIG. 19A, although there is exemplified a process inwhich the temperature is lowered to room temperature after thecrystallizing step, it is also possible to carry out thegettering+bonding step by directly raising the temperature after the endof crystallization. Even if such a process is carried out, the crystalsilicon film of the present invention can be obtained.

The thus obtained crystal silicon film (FIG. 18B) of the presentinvention has a feature that the number of defects in crystal grains isgreatly smaller than the crystal silicon film (FIG. 18A) in which merelycrystallization is carried out.

The difference in the number of defects appears as the difference inspin density by an electron spin resonance analysis (Electron SpinResonance: ESR). In the present circumstances, it is ascertained thatthe spin density of the crystal silicon film of the present invention isat most 5×10¹⁷ spins/cm³ (preferably 3×10¹⁷ spins/cm³ or less). However,since this measurement value is near the detection limit of an existingmeasuring device, it is expected that the actual spin density is lowerthan this value.

Findings as to Electrical Characteristics of a TFT

A TFT including an active layer of the foregoing CGS shows electricalcharacteristics comparable to a MOSFET using single crystal silicon.Data as set forth below are obtained from TFTs experimentally formed bythe present inventors.

(1) The subthreshold coefficient as an index showing switchingperformance (promptness in switching of on/off operation) of a TFT is assmall as 60 to 100 mV/decade (typically 60 to 85 mV/decade) for both anN-channel TFT and a P-channel TFT.

(2) The field effect mobility (μ_(FE)) as an index showing an operationspeed of a TFT is as large as 200 to 650 cm²/Vs (typically 250 to 300cm²/Vs) for an N-channel TFT, and 100 to 300 cm²/Vs (typically 150 to200 cm²/VS) for a P-channel TFT.

(3) The threshold voltage (V_(th)) as an index indicating a drivingvoltage of a TFT is as small as −0.5 to 1.5 V for an N-channel TFT and−1.5 to 0.5 V for a P-channel TFT.

As described above, it is ascertained that extremely superior switchingcharacteristics and high speed operation characteristics can berealized.

Findings as to Circuit Characteristics

Next, frequency characteristics by a ring oscillator employing TFTsmanufactured by using the CGS film will be described. The ringoscillator is a circuit in which an odd number of inverter circuits eachmade of a CMOS structure are connected like a ring, and is used forobtaining a delay time per inverter circuit. The structure of the ringoscillator used in experiments are as follows:

the number of stages: nine

the thickness of a gate insulating film of a TFT:30 nm and 50 nm

the gate length of a TFT:0.6 μm.

As the result of investigation of the oscillation frequency, it waspossible to obtain the oscillation frequency of 1.04 GHz at the maximumvalue. Moreover, a shift register as one of TEGs of LSI circuits wasactually manufactured and the operation frequency was ascertained. As aresult, the output pulse of operation frequency 100 MHz was obtained inthe shift resister in which the thickness of the gate insulating film is30 nm, the gate length is 0.6 μm, the power source voltage is 5 V, andthe number of stages is 50.

The above described surprising data of the ring oscillator and the shiftregister show that the TFT of the present invention has performancecomparable to or exceeding an IGFET using single crystal silicon.

Findings as to Relation Between TFT Characteristics and CGS

The superior TFT characteristics and circuit characteristics asdescribed above mainly depend on the fact that the CGS film havingcontinuity of crystal lattices at the crystal grain boundary is used asthe active layer of the TFT. The reason will be considered below.

The continuity of the crystal lattices at the crystal grain boundary iscaused from the fact that the crystal grain boundary is a grain boundarycalled “planar grain boundary”. The definition of the planar grainboundary is given as “Planar boundary” set forth in “Characterization ofHigh-Efficiency Cast-Si Solar Cell Wafers by MBIC Measurement; RyuichiShimokawa and Yutaka Hayashi, Japanese Journal of Applied Physics vol.27, No. 5, pp. 751-758, 1988”.

According to the above paper, the planar boundary includes {111} twingrain boundary, {111} lamination defect, {221} twin grain boundary,{221} twist grain boundary, and the like. The planar boundary has afeature that it is electrically inactive. That is, although the planarboundary is a crystal grain boundary, it does not function as a trap forblocking the movement of carriers, so that it can be regarded assubstantially not existing.

Particularly, the {111} twin grain boundary is also called acorresponding grain boundary of Σ3, and the {221} twin grain boundary isalso called a corresponding grain boundary of Σ9. The Σ value is aparameter which becomes an index showing the degree of conformity of acorresponding grain boundary. It is known that as the Σ value is small,the conformity of the crystal grain boundary is superior.

As the result of observation of the semiconductor thin film of thepresent invention in detail with the TEM performed by the presentapplicant, it was found that almost all crystal grains (90% or more,typically 95% or more) was the corresponding grain boundary of Σ3, thatis, the {111} twin grain boundary.

In the crystal grain boundary formed between two crystal grains, whenthe plane orientations of both the crystals are {110}, and if an angleformed by lattice stripes corresponding to the {111} plane is θ, it isknown that when θ is 70.5°, the boundary becomes the corresponding grainboundary of Σ3.

Thus, in the crystal grain boundary shown in the TEM photograph of FIG.16A, the respective lattice stripes of adjacent crystal grains arecontinuous at an angle of about 70°, so that it is easily inferred thatthis crystal grain boundary is the {111} twin crystal grain boundary.

Incidentally, when θ is 38.9°, the boundary becomes the correspondinggrain boundary of Σ9. Such other crystal grain boundary also existed.

Such a corresponding grain boundary is formed only between crystalgrains of the same plane orientation. That is, since the planeorientation of the semiconductor thin film of the present invention isuniform roughly as {110}, such a corresponding grain boundary can beformed over a wide range. This feature can not be obtained by otherpolysilicon films in which the plane orientation is irregular.

FIG. 20A is a TEM photograph (dark field image) of a semiconductor thinfilm of the present invention, which is magnified 15 thousands times.Although white regions and black regions are seen in the photograph,portions of the same color have the same orientation.

The remarkable feature in FIG. 20A is that in the dark field image ofsuch a wide range, the white regions are continuously united at a ratherhigh rate. This means that crystal grains having the same orientationexist with some directionality, and adjacent crystal grains have almostthe same orientation.

On the other hand, FIG. 20B is a TEM photograph (dark field image) inwhich a conventional high temperature polysilicon film is magnified 15thousands times. In the conventional high temperature polysilicon film,portions of the same plane orientation merely exist at random, and theuniformity with directionality as shown in FIG. 20A can not beascertained. It is conceivable that this is caused from irregularity oforientation of adjacent crystal grains.

By repeating observations and measurements over a number of regionsother than the measured points shown in FIG. 16A, the present applicantascertains that the continuity of the crystal lattices at the crystalgrain boundary is maintained in a sufficiently wide region formanufacturing a TFT.

The present invention having the above described structure will bedescribed in more detail with specific embodiments shown below.

Embodiment 1

In this embodiment, manufacturing steps of a semiconductor device havingthe structure of the present invention will be described with referenceto FIGS. 4A to 4D. Specifically, there is shown an example in which adriving circuit constituted by CMOS circuits in which an NTFT (N-channelTFT) and a PTFT (P-channel TFT) using a polysilicon film arecomplementarily combined, and a pixel matrix circuit constituted byNTFTs are integrally formed on the same substrate.

First, in accordance with the manufacturing steps explained by usingFIGS. 1A to 1D, a crystalline silicon film (typically, polycrystalsilicon film) 105 is formed. Then the polycrystal silicon film 105 ispatterned to form active layers 403 to 405. At this time, although thepolycrystal silicon film formed on the side surface of a crystallizedglass 401 is removed, the polycrystal silicon film on the back surfaceremains as it is.

Reference numeral 403 denotes the active layer of the PTFT of the CMOScircuit, 404 denotes the active layer of the NTFT of the CMOS circuit,and 405 denotes the active layer of the pixel matrix circuit, and thethickness of each layer is 50 nm.

The crystallized glass 401 used in this embodiment has the compositionof SiO₂: 65%, Al₂O₃: 25%, MgO: 10%, and ZrO₂: 10%. This crystallizedglass 401 has a feature that it is transparent. Reference numeral 402denotes a silicon oxide film obtained by thermal oxidation of anamorphous silicon film, and the thickness thereof is 400 nm.

In this way, the state of FIG. 4A is obtained. Next, a thermal oxidationstep is carried out at a temperature of 1000° C. to form gate insulatingfilms 406 to 408 made of thermal oxidation films with a thickness of 50nm. The processing atmosphere may be a dry O₂ atmosphere or a wet O₂atmosphere. It does not matter if a silicon nitride oxide film, asilicon nitride film, or the like is formed on the thermal oxidationfilm so that the gate insulating film is made of a lamination structure.

It is also possible to form a silicon nitride oxide film by a lowpressure CVD method using silane (SiH₄) and nitrous oxide (N₂O) as afilm forming gas and to utilize the film as the gate insulting film. Itis appropriate that the temperature of film formation is made 800 to900° C.

Further, it is also effective to form a silicon oxide film, a siliconnitride film, or a silicon nitride oxide film by a plasma CVD method, asputtering method, or a low pressure CVD method, and thereafter, athermal oxidation step is carried out. In this case, a thermal oxidationreaction progresses at an interface between the active layers and theforegoing insulating film. This structure is effective for preventingbreakdown of the gate insulating film by an edge thinning phenomenon(phenomenon in which a thermal oxidation film becomes extremely thin atan end of an active layer).

After the gate insulating films 406 to 408 are formed in this way, apolycrystal silicon film having N-type conductivity is formed, andpatterning is carried out by using resist masks 409 to 411 as masks toform gate electrodes 412 to 414. At this time, over etching is carriedout after the pattern formation to etch the side surfaces of the gateelectrodes by 500 nm to 1.5 μm (typically 800 nm to 1 μm).

As shown in FIG. 4B, an adding step of phosphorus (or arsenic is alsoavailable) is carried out in such a state that the resist mask 409 to411 become like umbrellas. This adding step is carried out by an ionimplantation method or a plasma doping method. In this way, phosphorusadded regions 415 to 420 containing phosphorus with a concentration of1×10²⁰ to 1×10²¹ atoms/cm³ are formed.

Next, a resist mask 421 is formed to overlap with the resist masks 409to 411 so that only a region which becomes the PTFT is exposed. Sincethe resist masks 409 to 411 are hardened by the adding step ofphosphorus, they are not removed at the development of the resist mask421.

After the state of FIG. 4C is obtained in this way, an adding step ofboron is carried out in the same manner as that of phosphorus. Since itis necessary to invert the phosphorus added regions 415 and 416 into a Ptype by this step, it is preferable to add boron with a concentration atleast three times as the concentration of phosphorus. In this way, boronadded regions 422 and 423 are formed.

After all the foregoing doping steps are ended, furnace annealing iscarried out at a temperature of 600 to 900° C. for 0.5 to 8 hours, sothat the added impurities are activated. This step may be carried out bylaser annealing or lamp annealing, which may be combined with thefurnace annealing.

Regions 417 and 418 formed by the above steps become a drain region anda source region of the NTFT constituting the CMOS circuit, respectively.Regions 419 and 420 become a source region and a drain region of theNTFT constituting the pixel matrix circuit, respectively. Regions 422and 423 become a source region and a drain region of the PTFTconstituting the CMOS circuit, respectively.

Regions (undoped regions) 424 to 426 in which the impurities were notadded become intrinsic or substantially intrinsic regions. The phrase“substantially intrinsic” means that the concentration of an impuritygiving an N type or a P type is not larger than the spin density, or theconcentration of the impurity is within the range of 1×10¹⁴ to 1×10¹⁷atoms/cm³.

In these undoped regions 424 to 426, a portion to which a gate voltageis applied functions as a channel formation region, and a portion towhich the gate voltage is not applied functions as an offset region.

Next, a first interlayer insulating film 427 made of a lamination filmof a silicon nitride film with a thickness of 25 nm and a silicon oxidefilm with a thickness of 900 nm is formed. Then source electrodes 428 to430, and drain electrodes 431 and 432 made of lamination films ofTi/Al/Ti (in this order, the thickness is 100/500/100 nm) are formed.

Next, a second interlayer insulating film made of a lamination structureof a silicon nitride film 433 with a thickness of 50 nm, a silicon oxidefilm (not shown) with a thickness of 20 nm, and a polyimide film 434with a thickness of 1 μm is formed. Instead of polyimide, other organicresin film of acryl, polyamide, or the like may be used. The siliconoxide film with a thickness of 20 nm in this case functions as anetching stopper when the polyimide film 434 is dry-etched.

After the second interlayer insulating film is formed, the polyimidefilm 434 is etched at a region where auxiliary capacitance issubsequently formed, so that an opening portion 435 is provided. At thistime, only the silicon nitride film 433 is made to remain on the bottomof the opening portion 435 or both the silicon nitride film 433 and thesilicon oxide film (not shown) are made to remain (FIG. 5A).

Then a titanium film with a thickness of 300 nm is formed, andpatterning is carried out to form a black mask 436. This black mask 436is disposed over the pixel matrix circuit and a portion which requiresshading, such as a TFT and wiring portion (FIG. 5B).

At this time, at the foregoing opening portion 435, the drain electrode432 of the pixel matrix circuit is positioned near the black mask 436through the intervening silicon nitride film 433 (or the lamination filmof the silicon nitride film and the silicon oxide film). In thisembodiment, the black mask 436 is kept at a fixed potential, and anauxiliary capacitance 437 including the drain electrode 432 as a lowerelectrode and the black mask 436 as an upper electrode is formed. Inthis case, since the dielectric is very thin and its relative dielectricconstant is high, large capacitance can be secured.

After the black mask 436 and the auxiliary capacitance 437 are formed inthis way, a polyimide film with a thickness of 1 μm is formed to form athird interlayer insulating film 438. Then the third interlayerinsulating film 438 is etched to form a contact hole (not shown).

At this time, at the point of time when the resist mask for theformation of the contact hole is formed, the polycrystal silicon filmremaining on the back surface of the substrate is removed by a dryetching method. Since the substrate is protected by the resist mask,even if the substrate is set in a chamber while the front surface sideof the substrate is made down, the component forming surface is notdamaged.

Next, a pixel electrode 439 made of a transparent conductive film(typically ITO) and having a thickness of 120 nm is formed on the thirdinterlayer insulating film 438 (FIG. 5c).

Finally, a heat treatment in a hydrogen atmosphere is carried out at350° C. for about two hours to hydrogenate the entire of the component.In this way, an active matrix substrate as shown in FIG. 5C iscompleted. Subsequently, a liquid crystal layer is held between theactive matrix substrate and an opposite substrate by a well-known cellassembling step, so that an active matrix type liquid crystal displaydevice (transmission type) is completed.

The structure of the active matrix substrate is not limited to thisembodiment, but any structure may be adopted. That is, as long as thestructure satisfies the structural conditions of the present invention,a user can freely design a TFT structure, a circuit arrangement, and thelike.

For example, although the transparent conductive film is used as thepixel electrode in this embodiment, if this film is changed to amaterial having high reflectivity, such as aluminum alloy film, areflection type active matrix liquid crystal display device can beeasily realized. In this case, it is not necessary that the crystallizedglass as the base of the active matrix substrate is transparent, but ashading substrate may be used.

Embodiment 2

In this embodiment, manufacturing steps of a semiconductor device havingthe structure of the present invention will be described with referenceto FIGS. 6A to 6D. Specifically, there is shown an example in which adriving circuit and a logic circuit constituted by CMOS circuits inwhich an NTFT (N-channel TFT) and a PTFT (P-channel TFT) using CGS arecomplementarily combined, and a pixel matrix circuit constituted byNTFTs are integrally formed on the same substrate.

The logic circuit is a signal processing circuit having functionsdifferent from those of a driving circuit typified by a shift registeror the like, and is a general term of a circuit for performing suchsignal processing as is conventionally carried out by an external IC,such as a D/A converter circuit, a memory circuit, a γ correctioncircuit, a calculation processing circuit, and the like.

First, in accordance with the manufacturing steps explained by usingFIGS. 2A to 2E, steps up to the gettering step of the catalytic elementare ended. Then active layers 603 to 605 made of only lateral growthregions are formed. Reference numeral 603 denotes the active layer ofthe PTFT of the CMOS circuit, 604 denotes the active layer of the NTFTof the CMOS circuit, and 605 denotes the active layer of the pixelmatrix circuit, and adjustment is made so that the thickness of eachlayer becomes 30 nm.

In this embodiment, a crystallized glass 601 has the composition ofSiO₂: 65%, Al²O₃: 25%, MgO: 10%, and ZrO₂: 10%. This crystallized glass601 has a feature that it is transparent. Reference numeral 602 denotesa silicon oxide film obtained by thermal oxidation of an amorphoussilicon film, and the thickness thereof is 400 nm.

In this way, the state of FIG. 6A is obtained. Next, a gate insulatingfilm 606 made of a silicon oxide film and having a thickness of 120 nmis formed. A silicon nitride oxide film or a silicon nitride film may beused. Further, it is also possible to adopt a lamination structure byfreely combining these insulating films.

After the gate insulating film 606 is formed, in the same state, athermal oxidation step is carried out within a temperature range of 800to 1000° C. (preferably 900 to 950° C.). At this time, since a thermaloxidation reaction progresses at an interface between the active layerand the gate insulating film, the active layer is made thin, and thethickness of the gate insulating film is increased. This structure iseffective in preventing breakdown of the gate insulating film due to anedge thinning phenomenon (phenomenon in which a thermal oxidation filmbecomes extremely thin at an end of an active layer).

At this time, although an atmosphere of the heat treatment may be anoxidizing atmosphere, if the heat treatment is carried out in anatmosphere containing a halogen element (typically, hydrogen chloride),the heat treatment becomes more effective. This is because it isconceivable that chlorine (Cl) produced by decomposition of hydrogenchloride has an effect of decreasing an interfacial level between theactive layer and the gate insulating film.

When the heat treatment within the temperature range of 800 to 1000° C.is carried out, the film quality of the gate insulating film itself isimproved.

Next, gate electrodes 607 to 609 made of crystalline silicon filmshowing N-type conductivity are formed on the gate insulating film 606.It is appropriate that the thickness of the gate electrodes 607 to 609is selected within the range of 200 to 300 nm (FIG. 6B).

After the gate electrodes 607 to 609 are formed, the gate insulatingfilm 606 is etched with the gate electrodes 607 to 609 as masks by a dryetching method. In this embodiment, a CHF₃ gas is used for etching thesilicon oxide film.

This step forms such a state that the gate insulating film remains atonly a portion just under the gate electrode (and gate wiring). Ofcourse, part remaining under the gate electrode is the part whichactually functions as the gate insulating film.

Next, a region which becomes the PTFT is concealed with a resist mask610, and an impurity (in this embodiment, phosphorus) giving an N typeis added by an ion implantation method or a plasma doping method. Sincepart of low concentration impurity regions 611 and 612 formed at thistime subsequently becomes an LDD (Lightly Doped Drain) region,phosphorus with a concentration of 1×10¹⁷ to 5×10¹⁸ atoms/cm³ is added(FIG. 6C).

Next, after the resist mask 610 is removed, a region which becomes theNTFT is concealed with a resist mask 613, and an impurity (in thisembodiment, boron) for giving a P type is added by an ion implantationmethod or a plasma doping method. Also at this time, a low concentrationimpurity region 614 is formed similarly to the case of phosphorus (FIG.6D).

After the state shown in FIG. 6D is obtained in this way, the resistmask 613 is removed, and then, side walls 615 to 617 are formed by usingan etch back method. In this embodiment, the side walls 615 to 617 areformed by using silicon nitride films.

In the case where the silicon oxide film is used as a material of theside wall, if the thickness of the silicon oxide film 602 for protectingthe side surface of the crystallized glass 601 is thin, there can occura case where the film disappears in the etch back step. Since the sidesurface of the glass is sufficiently smaller than the total area, theoutflow of glass constituents does not become a serious problem.However, it is effective that the thickness of the silicon oxide film602 is made thick in advance so that it remains even after the etch backstep.

After the side walls 615 to 617 are formed in this way, the region whichbecomes the PTFT is again concealed with a resist mask 618, andphosphorus is added. At this time, the dosage is made higher than theprevious adding step.

By the adding step of phosphorus, a source region 619, a drain region620, a low concentration impurity region (LDD region) 621, and a channelformation region 622 of the NTFT constituting the CMOS circuit aredefined. Moreover, a source region 623, a drain region 624, a lowconcentration impurity region (LDD region) 625, and a channel formationregion 626 of the NTFT constituting the pixel matrix circuit are defined(FIG. 7A).

Next, after the resist mask 618 is removed, the region which becomes theNTFT is concealed with a resist mask 627, and boron with a dosage higherthan the previous step is added. By this adding step of boron, a sourceregion 628, a drain region 629, a low concentration impurity region (LDDregion) 630, and a channel formation region 631 of the PTFT constitutingthe CMOS circuit are defined (FIG. 7B).

After the adding steps of impurities into the active layer are ended inthe manner described above, a heat treatment is carried out by furnaceannealing, laser annealing, or lamp annealing, so that the addedimpurities are activated. At this time, damages given to the activelayer at the addition of impurities are also recovered.

The channel formation regions 622, 626, and 631 are not added with anyimpurity element and are intrinsic or substantially intrinsic regions.Here, the phrase “substantially intrinsic” means that the concentrationof an impurity giving an N type or a P type is not higher than the spindensity of the channel formation region, or the concentration of theimpurity is within the range of 1×10¹⁴ to 1×10¹⁷ atoms/cm³.

Next, a first interlayer insulating film 632 made of lamination films ofa silicon nitride film with a thickness of 25 nm and a silicon oxidefilm with a thickness of 900 nm is formed. Then source electrodes 633 to635, and drain electrode 636 and 637 made of lamination films ofTi/Al/Ti (in this order, the thickness is 100/500/100 nm) are formed.

Next, a second interlayer insulating film made of a lamination structureof a silicon nitride film 638 with a thickness of 50 nm, a silicon oxidefilm (not shown) with a thickness of 20 nm, and a polyimide film 639with a thickness of 1 μm is formed. Instead of polyimide, other organicresin film of acryl, polyamide, or the like may be used. The siliconoxide film with a thickness of 20 nm in this case functions as anetching stopper when the polyimide film 639 is dry-etched.

After the second interlayer insulating film is formed, the polyimidefilm 639 is etched at a region where auxiliary capacitance issubsequently formed, so that an opening portion is provided. At thistime, only the silicon nitride film 638 is made to remain on the bottomof the opening portion or both the silicon nitride film 638 and thesilicon oxide film (not shown) are made to remain.

Then a titanium film with a thickness of 300 nm is formed, andpatterning is carried out to form a black mask 640. This black mask 640is disposed over the pixel matrix circuit and a portion which requiresshading, such as a TFT and a wiring portion.

At this time, in the foregoing opening portion, the drain electrode 637of the pixel matrix circuit is positioned near the black mask 640through the intervening silicon nitride film 638 (or the lamination filmof the silicon nitride film and the silicon oxide film). In thisembodiment, the black mask 640 is kept at a fixed potential, and anauxiliary capacitance 641 including the drain electrode 637 as a lowerelectrode and the black mask 640 as an upper electrode is formed. Inthis case, since the dielectric is very thin and the relative dielectricconstant is high, large capacitance can be secured.

After the black mask 640 and the auxiliary capacitance 641 are formed inthis way, a polyimide film with a thickness of 1 μm is formed to make athird interlayer insulating film 642. Then a contact hole is formed, anda pixel electrode 643 having a thickness of 120 nm and made of atransparent conductive film (typically ITO) is formed.

Finally, a heat treatment in a hydrogen atmosphere is carried out at350° C. for about two hours to hydrogenate the entire of the component.In this way, an active matrix substrate as shown in FIG. 7C iscompleted. Subsequently, when a liquid crystal layer is held between theactive matrix substrate and an opposite substrate by a well-known cellassembling step, an active matrix type liquid crystal display device(transmission type) is completed.

The structure of the active matrix substrate is not limited to thisembodiment, but any structure may be adopted. That is, as long as thestructure satisfies the structural conditions of the present invention,a user can freely design a TFT structure, a circuit arrangement, and thelike.

For example, although the transparent conductive film is used as thepixel electrode in this embodiment, if this film is changed to amaterial having high reflectivity, such as an aluminum alloy film, areflection type active matrix liquid crystal display device can beeasily realized. In this case, it is not necessary that the crystallizedglass as the base of the active matrix substrate is transparent, but ashading substrate may be used.

Embodiment 3

In this embodiment, an example in which an insulating silicon film forprotecting crystallized glass in the structure of Embodiment 1 is formedby a low pressure CVD method, will be described.

First, as a substrate, crystallized glass having the composition ofSiO₂: 52.5, Al₂O₃: 26.5, MgO: 11.9, TiO₂: 11.4 is prepared. This isnon-alkaline cordierite-based crystallized glass using TiO₂ as a nucleusforming agent.

Next, a silicon nitride oxide film is formed on the front surface, theback surface, and the side surface of the crystallized glass. In thisembodiment, the silicon nitride oxide film is formed by a low pressureCVD method using silane (SiH₄) and nitrous oxide (N₂O) as a film forminggas.

In this case, a film forming temperature is 800 to 850° C. (in thisembodiment, 850° C.), and the flow rates of the respective film forminggases are made SiH₄: 10 to 30 sccm and N₂O: 300 to 900 sccm. It isappropriate that the reaction pressure is made 0.5 to 1.0 torr.

If silane and nitrogen dioxide (NO₂) or nitrogen monoxide (NO) is usedas the film forming gas, it is also possible to form a silicon nitrideoxide film at a temperature of 600 to 650° C. In that case, the reactionpressure is made 0.1 to 1.0 torr, and the flow rates of the respectivegases are made SiH₄: 10 to 30 sccm and NO₂ or NO: 300 to 900 sccm.

In the case of this embodiment, since the silicon nitride oxide film isformed by the low pressure CVD method, the entire surface of thecrystallized glass is covered with the insulating film. If thedistortion point of the crystallized glass is 850° C. or less, it ispossible to take countermeasures against shrinkage at the same time asthe film formation.

If the film forming gas is made different, it is also possible to form asilicon nitride film as the protective film of the crystallized glass.In that case, it is appropriate that dichlorsilane (SiH₂Cl₂) of 40 to 50sccm and ammonia (NH₃) of 200 to 250 sccm are used as the film forminggases, the film forming temperature is made 750 to 800° C. and thereaction pressure is made 0.1 to 0.5 torr.

Although the silicon nitride film is the most suitable insulating filmfor blocking the outflow of glass constituents, since its stress isstrong, it has been unsuitable for a primer film of a TFT. However, inthe present invention, since the silicon nitride film is formed at leaston the front surface and the back surface of the crystallized glass, thestresses of the silicon nitride film at the back and the front of thesubstrate cancel each other out, so that a warp or the like of thesubstrate does not occur.

Embodiment 4

In this embodiment, an example in which an insulating silicon filmformed by a low pressure CVD method is used as a gate insulating film inEmbodiments 1 to 3, will be described. FIG. 8 is used for explanation.FIG. 8 shows the state immediately after a gate insulating film has beenetched since a gate electrode was formed.

In FIG. 8, reference numeral 801 denotes crystallized glass, and 802denotes a silicon nitride oxide film which becomes a protective film(primer film) for preventing the outflow of constituents from thecrystallized glass. Active layers 803 to 805 are formed at the surfaceside of the crystallized glass 801, and after the gate insulating filmis formed, gate electrodes 806 to 808 are formed.

Dry etching is carried out by using the gate electrodes 806 to 808 asmasks so that the gate insulating films 809 to 811 remain just under thegate electrodes.

The most important structure of this embodiment is to use the insulatingsilicon film (in this embodiment, silicon nitride oxide film) formed bythe low pressure CVD method as the gate insulating film. That is, thefeature is that the gate insulating film is also formed on all of thefront surface, the back surface, and the side surface of thecrystallized glass 801.

Thus, at the point of time (state of FIG. 8) when the etching step ofthe gate insulating film (silicon nitride oxide film) is ended, the filmon the front surface side of the substrate is completely removed exceptthe portions which are masked with the gate electrodes, and the siliconnitride oxide film 812 remains as it is on the back surface and the sidesurface of the substrate. Although the silicon nitride oxide film formedon the side surface is removed according to conditions, there is noproblem even if the film on the side surface is removed.

If the structure of this embodiment is used, even if the back surfaceand the side surface are exposed to an etchant or etching gas which canetch the silicon nitride oxide film in a subsequent step, it is possibleto make the silicon nitride oxide film 802, which was directly formed onthe crystallized glass 801, remain. That is, it is possible tothoroughly prevent the outflow of constituents from the glass substrate.

Embodiment 5

Although the crystalline silicon film showing N type conductivity isused as the gate electrode in Embodiments 1 and 2, any material may beused as long as the material has conductivity. Especially, in the casewhere a liquid crystal display device for direct viewing ismanufactured, since the area of a pixel matrix circuit becomes large, itis preferable to use a material having low wiring resistance.

In such a case, it is preferable to use aluminum or material mainlycontaining aluminum as the gate electrode. In this embodiment, analuminum film containing scandium of 2 wt % is used as the gateelectrode.

In the case where the material mainly containing aluminum is used as thegate electrode, it is appropriate that a technique set forth in JapanesePatent Application Laid-Open No. Hei. 7-135318 by the present inventorsbe used. In the publication, instead of the side wall used in Embodiment1, an anodic oxidation film obtained by anodic oxidation of the gateelectrode is used.

When aluminum or material mainly containing aluminum is used as the gateelectrode as in this embodiment, it becomes possible to form gate wiringwith low wiring resistance, and an active matrix substrate having highresponse speed can be manufactured.

This embodiment can be combined with structures of Embodiments 1 to 4.

Embodiment 6

In Embodiments 1 and 2, it is effective to add an impurity element forcontrolling a threshold voltage (Vth) into an active layer. Although ithas been already described that such an element can be added at the filmformation of an amorphous semiconductor thin film, it is sufficient ifthe element be added into at least a channel formation region, so thatthe element may be added anytime before formation of a gate electrode.

In the case where the element is added at a time other than the filmformation, it is possible to use such means as addition by an ionimplantation method or a plasma doping method, addition by diffusionfrom a vapor phase, or addition by diffusion from a solid phase.According to these means, selective addition is possible, for example,added impurities can be made different between an NTFT and a PTFT, sothat these means would be effective.

As the added impurity element, when Vth is moved to a plus side, anelement in group 13 (boron, gallium, or indium) is used, and when Vth ismoved to a minus side, an element in group 15 (phosphorus, arsenic, orantimony) is used.

This embodiment may be combined with structures of Embodiments 1 to 5.

Embodiment 7

Although the explanation has been made in Embodiments 1 to 6 by using atop gate type TFT (planar type TFT) as an example, the structure of thepresent invention can be applied to a bottom gate type TFT (typically,reverse stagger type TFT) by using CGS. In this embodiment, an examplein which the structure of the present invention is applied to thereverse stagger type TFT, will be described with reference to FIG. 9.

In FIG. 9, reference numeral 901 denotes crystallized glass, 902 denotesa silicon oxide film obtained by thermal oxidation of an amorphoussilicon film, which is formed so as to cover the entire surface of thesubstrate. Reference numeral 903 denotes a gate electrode in whichtantalum (Ta) and tantalum nitride (TaN) are laminated.

In the case of this embodiment, since a gettering process of a catalyticelement to an active layer is carried out after the gate electrode 903is formed, a material having heat resistance so as to be capable ofresistance to a heating process exceeding 700° C. is used for the gateelectrode 903. As such a material, in addition to tantalum, there may beenumerated chromium, tungsten, molybdenum, and crystalline silicon filmhaving conductivity.

Next, a gate insulating film 904 is formed on the gate electrode 903. Inthis embodiment, a silicon nitride oxide film is formed by a lowpressure CVD method to be made the gate insulating film. Thus, the gateinsulating film 904 is formed not only on the front surface of thesubstrate but also on the back surface and the side surface of thesubstrate, so that the film covers the entire of the substrate.

An active layer constituted by a source region 905, a drain region 906,a low concentration impurity region (LDD region) 907, and a channelformation region 908 is formed on the gate insulating film 904. In thecase of this embodiment, the source/drain regions are formed by an ionimplantation method or a plasma doping method. Of course, addition maybe carried out by diffusion using a vapor phase method or a solid phasemethod.

Reference numeral 909 denotes a channel protective film, which is formedof an insulating silicon film. In the case of this embodiment, thechannel protective film 909 not only protects the channel formationregion 908 but also is utilized as a doping mask for forming thesource/drain regions and the low concentration impurity region.

Specifically, the channel protective film is first formed on a portionwhich becomes the low concentration impurity region and the, channelformation region, and an impurity is added by using the channelprotective film as a mask so that the source/drain regions are formed.Thereafter, the channel protective film is removed except a part on theportion which becomes the channel formation region, and the lowconcentration impurity region is formed by subsequent impurity addition.

After the impurity addition into the active layer is ended, a thermalannealing step is carried out by using one of furnace annealing, laserannealing, and lamp annealing or combination of those, so that theimpurity is activated. At that time, the channel protective film 909remaining as it is even after the impurity addition step was carried outhas an effect of preventing the impurity from diffusing into the channelformation region from the source/drain regions or the low concentrationimpurity region.

Next, as an interlayer insulating film 910, an acrylic film with athickness of 2 μm is formed. Of course, other organic resin films suchas polyimide may be used. In this case, the channel protective film 909prevents the direct contact between the interlayer insulating film 910made of the acrylic film and the channel formation region 908, so thatthe film can block the change of TFT characteristics due to organicpollution.

A contact hole is formed in the interlayer insulating film 910, a sourceelectrode 911 and a drain electrode 912 made of a material containingaluminum as the main ingredient are formed, and finally, hydrogenatingis carried out so that the reverse stagger type TFT as shown in FIG. 9is completed.

Although only the manufacturing steps of a single body of the reversestagger type TFT have been described in this embodiment, since it iseasy to constitute a CMOS circuit or a pixel matrix circuit with thereverse stagger type TFT of this embodiment when referring to themanufacturing steps of Embodiment 1, the explanation will be omitted.

Thus, it is easy to complete an active matrix substrate by using reversestagger type TFTs such as shown in this embodiment and to realize anactive matrix type liquid crystal display device.

Embodiment 8

Although the explanation has been made in Embodiments 1 to 6 by using atop gate type TFT (planar type TFT) as an example, the structure of thepresent invention can be applied to a bottom gate type TFT (typically, areverse stagger type TFT) by using a high temperature polysilicon. Inthis embodiment, an example in which the structure of the presentinvention is applied to the reverse stagger type TFT will be describedwith reference to FIG. 10.

In FIG. 10, reference numeral 1001 denotes crystallized glass, and 1002denotes a silicon oxide film obtained by thermal oxidation of anamorphous silicon film, which is formed so as to cover the entiresurface of the substrate. Reference numeral 1003 denotes a gateelectrode in which tantalum (Ta) and tantalum nitride (TaN) arelaminated.

In the case of this embodiment, a material having heat resistance so asto be capable of resistance to a heating process at a temperatureexceeding at least 750° C. is used for the gate electrode 1003. As sucha material, other than tantalum, there are enumerated, chromium,tungsten, molybdenum, and crystalline silicon film having conductivity.

Next, a gate insulating film 1004 is formed on the gate electrode 1003.In this embodiment, a silicon nitride oxide film is formed by a lowpressure CVD method to be made the gate insulating film. Thus, the gateinsulating film 1004 is formed not only on the front surface of thesubstrate but also on the back surface and the side surface of thesubstrate, so that the film covers the entire of the substrate.

An active layer constituted by a source region 1005, a drain region1006, a low concentration impurity region (LDD region) 1007, and achannel formation region 1008 is formed on the gate insulating film1004. In the case of this embodiment, the source/drain regions areformed by an ion implantation method or a plasma doping method. Ofcourse, addition may be carried out by diffusion using a vapor phasemethod or a solid phase method.

Reference numeral 1009 denotes a channel protective film, which is madeof an insulating silicon film. In the case of this embodiment, thechannel protective film 1009 not only protects the channel formationregion 1008 but also is utilized as a doping mask for forming thesource/drain regions and the low concentration impurity region.

Specifically, the channel protective film is first formed on a portionwhich becomes the low concentration impurity region and the channelformation region, and an impurity is added by using the channelprotective film as a mask so that the source/drain regions are formed.Thereafter, the channel protective film is removed except a part on theportion which becomes the channel formation region, and the lowconcentration impurity region is formed by subsequent impurity addition.

After the impurity addition into the active layer is ended, a thermalannealing step is carried out by using one of furnace annealing, laserannealing, and lamp annealing or combination of those, so that theimpurity is activated. At that time, the channel protective film 1009remaining as it is even after the impurity addition step was carried outhas an effect of preventing the impurity from diffusing into the channelformation region from the source/drain regions or the low concentrationimpurity region.

Next, as an interlayer insulating film 1010, an acrylic film with athickness of 2 μm is formed. Of course, other organic resin films suchas polyimide may be used. In this case, the channel protective film 1009prevents the direct contact between the interlayer insulating film 1010made of the acrylic film and the channel formation region 1008, so thatthe film can block the change of TFT characteristics due to organicpollution.

Then contact holes are formed in the interlayer insulating film 1010, asource electrode 1011 and a drain electrode 1012 made of a materialcontaining aluminum as the main ingredient are formed, and finally,hydrogenating is carried out so that the reverse stagger type TFT asshown in FIG. 10 is completed.

Although only the manufacturing steps of a single body of the reversestagger type TFT have been described in this embodiment, since it iseasy to constitute a CMOS circuit or a pixel matrix circuit with thereverse stagger type TFT of this embodiment when referring to themanufacturing steps of Embodiment 1, the explanation will be omitted.

Thus, it is easy to complete an active matrix substrate by using reversestagger type TFTs such as shown in this embodiment and to realize anactive matrix type liquid crystal display device.

Embodiment 9

In the step shown in FIG. 2E, although the heat treatment in theatmosphere containing the halogen element is carried out as thegettering means of the catalytic element, in this embodiment, an examplein which the catalytic element is removed by another means will bedescribed with reference to FIGS. 11A to 11C.

After the steps of FIGS. 2A to 2D are ended, the mask insulating film205 is again patterned to form new opening portions 1101 (FIG. 11A).

Next, an element (in this embodiment, phosphorus) selected from group 15is added. It is appropriate that the concentration of the addition atthis time be 1×10¹⁹ to 1×10²¹ atoms/cm³. Here, a plasma doping method isused as a means for adding phosphorus.

By this adding step of phosphorus, phosphorus with a high concentrationis added into regions exposed in the opening portions 1101. In thepresent specification, the regions 1102 will be referred to as getteringregions. Regions 1103 which are masked with the mask insulating films205 so that phosphorus was not added will be referred to as getteredregions (FIG. 11B).

Next, as shown in FIG. 11C, within the temperature range of 600 to 800°C., a heat treatment is carried out for 2 to 24 hours, so that thecatalytic elements contained in the gettered regions 1103 are moved intothe gettering regions 1102. This is a phenomenon using the getteringeffect of phosphorus for a metallic element. If a process temperature islower than 600° C., the gettering performance is extremely lowered, andif the process temperature exceeds 800° C., phosphorus is reverselydiffused into the gettered regions 1103. Thus, such temperature levelsare not preferable.

When the catalytic element is captured into the gettering regions 1102in the manner as described above, the concentration of the catalyticelement remaining after the process in the gettered regions 1104 islowered to 5×10¹⁷ atoms/cm³ or less. Subsequently, it is satisfactory ifthe gettering regions are completely removed by etching when an activelayer is formed.

The structure of this embodiment can be combined with any structure ofEmbodiments 1 to 10. Even if the manufacturing steps of this embodimentare used, the foregoing CGS film can be formed.

Embodiment 10

In Embodiments 1 and 2, although the manufacturing steps of a planartype TFT having an offset structure has been described, a planar typeTFT having an LDD structure may be adopted. In that case, for example, atechnique set forth in Japanese Patent Application Laid-Open No. Hei.6-265940 may be used, or other well-known methods may be used for theformation of the TFT.

The structure of this embodiment can be combined with any structure ofEmbodiments 1 to 4 or 6.

Embodiment 11

In this embodiment, the pixel structure of the active matrix substrateshown in FIG. 6C will be described more specifically. FIG. 12A is a viewshowing a sectional structure of a pixel TFT and FIG. 12B is a top viewthereof. In FIGS. 12A and 12B, reference numeral 21 denotes an activelayer, 22 denotes a gate line, 23 denotes a source line, 24 denotes adrain electrode, 25 denotes a black mask, and 26 denotes a contact holefor connecting the drain electrode 24 to a pixel electrode 27.

The feature of this embodiment is to form an auxiliary capacitance overthe pixel TFT and between the drain electrode 24 and the black mask 25.

FIG. 12B shows the structure of the pixel TFT viewed from above.Incidentally, FIG. 12A corresponds to a sectional view of FIG. 12B takenalong line A-A′. Common reference characters are used in FIGS. 12A and12B.

Like this, the drain electrode 24 is formed in such an arrangement thatit overlaps with the gate line 22, and an auxiliary capacitance isformed between the drain electrode 24 and a black mask 25 oppositethereto through an intervening dielectric 28. In this embodiment, as thedrain electrode 24, a three-layer structure in which a titanium film issandwiched between aluminum films is adopted.

In the case of this embodiment, after the drain electrode 24 is formed,an interlayer insulating film made of a three-layer structure of asilicon nitride film/silicon oxide film/acrylic film is formed, and theblack mask 25 is formed thereon.

At this time, before formation of the black mask 25, only the acrylicfilm at a region which subsequently becomes the auxiliary capacitance isremoved to form an opening portion. Then, only the silicon oxide filmand the silicon nitride film remain on the bottom of the openingportion, and an insulating layer made of this two-layer structurefunctions as the dielectric 28 of the auxiliary capacitance.

Embodiment 12

FIG. 13 shows an example in which a liquid crystal display device isconstructed by employing an active matrix substrate ,utiiizing TFTs withthe use of CGS, having the structure shown in Embodiment 2, 4, 5, 6, 7,9, or 11. FIG. 13 shows a portion corresponding to the main body of theliquid crystal display device, which is also called a liquid crystalmodule.

In FIG. 13, reference numeral 1301 denotes crystallized glass, and 1302denotes an insulating silicon film formed so as to cover the entiresurface of the crystallized glass. In the case where a plurality ofactive matrix substrates are made by cutting from a large substrate in amultiple-chamfered manner, although the insulating silicon film does notexist on the side surface that is a cut surface, the insulating siliconfilm remains on other side surfaces than the above, which is the featureof the present invention. Of course, since the substrate is completed asthe active matrix substrate, even if it is not protected with theinsulating silicon film, there is no fear that the constituents may beflown out.

On the substrate of such structure, a plurality of TFTs are formed ofsemiconductor thin films having the feature that crystal grainboundaries do not substantially exist. These TFTs constitute on thesubstrate a pixel matrix circuit 1303, a gate side driving circuit 1304,a source side driving circuit 1305, and a logic circuit 1306. Anopposite substrate 1307 is bonded to such an active matrix substrate. Aliquid crystal layer (not shown) is held between the active matrixsubstrate and the opposite substrate 1307.

In the structure shown in FIG. 13, it is desirable that all sides of theactive matrix substrate are flush with all sides of the oppositesubstrate except one side. By this, the number of products obtained froma large substrate can be effectively increased. In the above-mentionedone side, a part of the opposite substrate is removed so that a part ofthe active matrix substrate is exposed, and an FPC (Flexible PrintCircuit) 1308 is attached thereto. As the need arises, an IC chip(semiconductor circuit constituted by MOSFETs formed on single crystalsilicon) may be mounted thereon.

Since the TFT including an active layer of the semiconductor thin filmused in the present invention has an extremely high operation speed, itis possible to integrally form a signal processing circuit driven at ahigh frequency of several hundreds MHz to several GHz on the samesubstrate as a pixel matrix circuit. That is, the liquid crystal moduleshown in FIG. 13 materializes a system-on-panel.

Although this embodiment shows an example in which the present inventionis applied to the liquid crystal display device, it is also possible toform an active matrix type EL (electroluminescence) display device orthe like. It is also possible to form an image sensor or the like havinga photoelectric conversion layer on the same substrate.

Incidentally, the electrooptical device is defined as a device havingfunctions for converting an electric signal into an optical signal orfor converting an electric signal into an optical signal, such as theforegoing liquid crystal display device, the EL display device, and theimage sensor. The present invention can be applied to any electroopticaldevice as long as the device can be formed by using a semiconductor thinfilm on a substrate having an insulating surface.

Embodiment 13

An example in which a liquid crystal display device is constructed byemploying an active matrix substrate using TFTs having the structureshown in Embodiment 1, 3, 4, 5, 6, 8, 10, or 13 and using hightemperature polysilicon, will be described with reference to FIGS. 14Aand 14B. FIGS. 14A and 14B respectively, show a portion corresponding tothe main body of the liquid crystal display device, which is also calleda liquid crystal module.

In FIG. 14A, reference numeral 1401 denotes crystallized glass, and 1402denotes an insulating silicon film formed on the entire surface of thecrystallized glass. In the case where a plurality of active matrixsubstrates are made by cutting from a large substrate in amultiple-chamfered manner, although the insulating silicon film does notexist on the side surface that is a cut surface, the insulating filmremains on other side surfaces than the above, which is the feature ofthe present invention. Of course, since the substrate is completed asthe active matrix substrate, even if it is not protected with theinsulating silicon film, there is no fear that the constituents may beflown out.

On the substrate of such structure, a plurality of TFTs are formed ofpolycrystal silicon films (high temperature polysilicon films) formed byusing high temperature annealing. These TFTs constitute on the substratea pixel matrix circuit 1403, a gate side driving circuit 1404, and asource side driving circuit 1405. An opposite substrate 1406 is bondedto such an active matrix substrate. A liquid crystal layer (not shown)is held between the active matrix substrate and the opposite substrate1406.

In the structure shown in FIG. 14A, it is desirable that all sides ofthe active matrix substrate are made flush with all sides of theopposite substrate except one side. By this, it is possible toeffectively increase the number of multiple-chamfers cut from a largesubstrate. In the above-mentioned one side, a part of the oppositesubstrate is removed so that a part of the active matrix substrate isexposed, and an FPC (Flexible Print Circuit) 1407 is attached thereto.

In FIG. 14A, IC chips (semiconductor circuits constituted by MOSFETsformed on single crystal silicon) 1408 and 1409 are mounted byeffectively using the space where the FPC 1407 is attached. These ICchips 1408 and 1409 carry out signal processing (digital/analogconversion, storing of information, γ correction, and the like)necessary for driving the liquid crystal module.

As shown in FIG. 14B, it is also possible to carry out signalprocessing, such as processing performed by the IC chips 1408 and 1409in FIG. 14A, by a logic circuit 1410 formed of TFTs on the samesubstrate. Since the high temperature polysilicon film is very excellentin crystallinity, it is possible to form a circuit having a highoperation speed, such as a logic circuit. That is, the liquid crystalmodule shown in FIG. 14B materializes a system-on-panel.

Although this embodiment shows an example in which the present inventionis applied to the liquid crystal display device, it is also possible toform an active matrix type EL (electroluminescence) display device. Itis also possible to form an image sensor or the like having aphotoelectric conversion layer on the same substrate.

Incidentally, the electrooptical device is defined as a device havingfunctions for converting an optical signal into an electric signal orfor converting an electric signal into an optical signal, such as theforegoing liquid crystal display device, the EL display device, and theimage sensor. The present invention can be applied to any electroopticaldevice as long as the device can be formed by using a semiconductor thinfilm on a substrate having an insulating surface.

Embodiment 14

In the present invention, not only the electrooptical device as shown inEmbodiments 12 and 13 but also a thin film integrated circuit (orsemiconductor circuit) in which functional circuits are integrated, maybe formed. For example, it is also possible to form a calculationcircuit such as a microprocessor, a high frequency circuit (MMIC:Microwave Module IC) for a portable equipment, or the like.

Moreover, by using the merits of a TFT using a thin film, it is alsopossible to form a semiconductor circuit of a three-dimensionalstructure to form a VLSI circuit integrated with ultra high density.Like this, it is possible to form a semiconductor circuit havingextremely added functionality by using the TFTs of the presentinvention. Incidentally, in the present specification, the semiconductorcircuit is defined as an electric circuit for controlling and convertingelectric signals by using semiconductor characteristics.

Embodiment 15

In this embodiment, examples of electronic equipments (applied products)having an electrooptical device or a semiconductor circuit shown inEmbodiments 12 to 14 will be described with reference to FIGS. 15A to15F. Incidentally, the electronic equipment is defined as a producthaving a semiconductor circuit and/or an electrooptical device.

As the electronic equipments to which the present invention can beapplied, a video camera, an electric still camera, a projector, a headmount display, a car navigation system, a personal computer, a portableinformation terminal (mobile computer, portable telephone, PHS (PersonHandyphone System), etc.) and the like are enumerated.

FIG. 15A shows a portable telephone which is constituted by a main body2001, an audio output portion 2002, an audio input portion 2003, adisplay device 2004, an operation switch 2005, and an antenna 2006. Thepresent invention can be applied to the audio output portion 2002, theaudio input portion 2003, the display device 2004, and the like.

FIG. 15B shows a video camera which is constituted by a main body 2101,a display device 2102, an audio input portion 2103, an operation switch2104, a battery 2105, and an image receiving portion 2106. The presentinvention can be applied to the display device 2102, the audio inputportion 2103, the image receiving portion 2106, and the like.

FIG. 15C shows a mobile computer which is constituted by a main body2201, a camera portion 2202, an image receiving portion 2203, anoperation switch 2204, and a display device 2205. The present inventioncan be applied to the camera portion 2202, the image receiving portion2203, the display device 2205, and the like.

FIG. 15D shows a head mount display which is constituted by a main body2301, a display device 2302, and a band portion 2303. The presentinvention can be applied to the display device 2302.

FIG. 15E shows a rear type projector which is constituted by a main body2401, a light source 2402, a display device 2403, a polarizing beamsplitter 2404, reflectors 2405 and 2406, and a screen 2407 The presentinvention can be applied to the display device 2403.

FIG. 15F shows a front type projector which is constituted by a mainbody 2501, a light source 2502, a display device 2503, an optical system2504, and a screen 2505. The present invention can be applied to thedisplay device 2503.

As described above, the scope of an application of the present inventionis very wide, and the present invention can be applied to electronicequipments of any field. Moreover, the present invention can be appliedto any product as long as it requires an electrooptical device or asemiconductor circuit.

The present invention adopts such structure that crystallized glasswhich is inexpensive and made large is used, and at least the frontsurface and the back surface (preferably the entire surface) of theglass are protected by insulating silicon films in order to utilizingthe crystallized glass with safety (without fear of pollution).

Then a TFT using a semiconductor thin film with a unique crystalstructure excellent in conformity of crystal grain boundaries ismanufactured on the crystallized glass, so that a system-on-panel isrealized and an electrooptical device or a semiconductor circuit withhigh performance, and further, an electronic equipment having them canbe provided at low cost.

What is claimed is:
 1. A method of manufacturing a semiconductor device,said method comprising the steps of: forming a first amorphoussemiconductor film comprising silicon over a front surface and a backsurface of a glass substrate having a distortion point of not lower than750° C.; carrying out a first heat treatment to oxidize the firstamorphous semiconductor film to form a first thermal oxidation film;forming a second amorphous semiconductor film comprising silicon overthe first thermal oxidation film formed over the front surface of theglass substrate; providing the second amorphous semiconductor film witha catalytic element for facilitating crystallization of the secondamorphous semiconductor film; carrying out a second heat treatment tocrystallize the second amorphous semiconductor film to form acrystalline semiconductor film; gettering the catalytic element from thecrystalline semiconductor film; and patterning the crystallinesemiconductor film after the gettering step to form an active layer andto form a second thermal oxidation film on a surface of the activelayer.
 2. A method according to claim 1, wherein the glass substrate isa crystallized glass substrate.
 3. A method according to claim 1,wherein the distortion point of the glass substrate is in a range of 950to 1100° C.
 4. A method according to claim 1, wherein the crystallinesemiconductor film is a silicon film.
 5. A method according to claim 1,wherein a heat treatment is carried out in an atmosphere containing ahalogen element at a temperature exceeding 700° C. in the getteringstep.
 6. A method according to claim 1, wherein the gettering stepfurther comprises the steps of: selectively adding an impurity elementselected from group 15 into a part of the crystalline semiconductor thinfilm; and moving the catalytic element remaining in a first region wherethe impurity element was not added into a second region where theimpurity element was added by a heat treatment.
 7. A method according toclaim 1, wherein the catalytic element comprises at least one selectedfrom the group consisting of Ni, Ge, Co, Fe, Pd, Pt, Cu, Au, and Pb. 8.A method according to claim 1, wherein the first semiconductor film isan amorphous silicon film.
 9. A method according to claim 1, wherein thefirst semiconductor film is formed over all surface of the glasssubstrate.
 10. A method according to claim 1, wherein the firstsemiconductor film is completely transformed into the first thermaloxidation film by the first heat treatment.
 11. A method according toclaim 1, wherein the first semiconductor film is formed through a lowpressure CVD method.
 12. A method according to claim 1, wherein thesecond semiconductor film further comprises germanium.
 13. A methodaccording to claim 1, wherein the semiconductor device is in combinationwith an electronic equipment, wherein the electronic equipment is oneselected from the group consisting of a portable telephone, a videocamera, a mobile computer, a head mount display, a rear type projector,a front type projector.
 14. A method according to claim 1, wherein thesecond amorphous semiconductor film is an amorphous silicon film.
 15. Amethod of manufacturing a semiconductor device, said method comprisingthe steps of: forming a first amorphous semiconductor film comprisingsilicon over a front surface and a back surface of a glass substratehaving a distortion point of not lower than 750° C.; carrying out afirst heat treatment to oxidize the first amorphous semiconductor filmto form a thermal oxidation film; forming a second amorphoussemiconductor film comprising silicon over the thermal oxidation filmformed over the front surface of the glass substrate; carrying out asecond heat treatment to crystallize the second amorphous semiconductorfilm to form a crystalline semiconductor film; and patterning thecrystalline semiconductor film to form an active layer.
 16. A methodaccording to claim 15, wherein the glass substrate is a crystallizedglass substrate.
 17. A method according to claim 15, wherein thedistortion point of the glass substrate is in a range of 950 to 1100° C.18. A method according to claim 15, wherein the crystallinesemiconductor film is a silicon film.
 19. A method according to claim15, wherein the first amorphous semiconductor film is an amorphoussilicon film.
 20. A method according to claim 15, wherein the firstsemiconductor film is formed over all surfaces of the glass substrate.21. A method according to claim 15, wherein the first semiconductor filmis completely transformed into the thermal oxidation film by the firstheat treatment.
 22. A method according to claim 15, wherein the firstsemiconductor film is formed through a low pressure CVD method.
 23. Amethod according to claim 15, wherein the second semiconductor filmfurther comprises germanium.
 24. A method according to claim 15, whereinthe semiconductor device is in combination with an electronic equipment,wherein the electronic equipment is one selected from the groupconsisting of a portable telephone, a video camera, a mobile computer, ahead mount display, a rear type projector, a front type projector.
 25. Amethod according to claim 15, wherein the second amorphous semiconductorfilm is an amorphous silicon film.
 26. A method of manufacturing anelectroluminescent display device, said method comprising the steps of:forming a first amorphous semiconductor film comprising silicon over afront surface and a back surface of a glass substrate having adistortion point of not lower than 7500° C.; carrying out a first heattreatment to oxidize the first amorphous semiconductor film to form afirst thermal oxidation film; forming a second amorphous semiconductorfilm comprising silicon over the first thermal oxidation film formedover the front surface of the glass substrate; providing the secondamorphous semiconductor film with a catalytic element for facilitatingcrystallization of the second amorphous semiconductor film; carrying outa second heat treatment to crystallize the second amorphoussemiconductor film to form a crystalline semiconductor film; getteringthe catalytic element from the crystalline semiconductor film: andpatterning the crystalline semiconductor film after the geftering stepto form an active layer and to form a second thermal oxidation film on asurface of the active layer.
 27. A method according to claim 26, whereinthe glass substrate is a crystallized glass substrate.
 28. A methodaccording to claim 26, wherein the distortion point of the glasssubstrate is in a range of 950 to 1100° C.
 29. A method according toclaim 26, wherein the crystalline semiconductor film is a silicon film.30. A method according to claim 26, wherein a heat treatment is carriedout in an atmosphere containing a halogen element at a temperatureexceeding 700° C. in the gettering step.
 31. A method according to claim26, wherein the gettering step further comprises the steps of:selectively adding an impurity element selected from group 15 into apart of the crystalline semiconductor film; and moving the catalyticelement remaining in a first region where the impurity element was notadded into a second region where the impurity element was added by aheat treatment.
 32. A method according to claim 26, wherein thecatalytic element comprises at least one selected from the groupconsisting of Ni, Ge, Co, Fe, Pd, Pt, Cu, Au, and Pb.
 33. A methodaccording to claim 26, wherein the first amorphous semiconductor film isan amorphous silicon film.
 34. A method according to claim 26, whereinthe first semiconductor film is formed over all surfaces of the glasssubstrate.
 35. A method according to claim 26, wherein the firstsemiconductor film is completely transformed into the first thermaloxidation film by the first heat treatment.
 36. A method according toclaim 26, wherein the first semiconductor film is formed through a lowpressure CVD method.
 37. A method according to claim 26, wherein thesecond semiconductor film further comprises germanium.
 38. A methodaccording to claim 26, wherein the electroluminescent display device isin combination with an electronic equipment, wherein the electronicequipment is one selected from the group consisting of a portabletelephone, a video camera, a mobile computer, a head mount display, arear type projector, a front type projector.
 39. A method according toclaim 26, wherein the second amorphous semiconductor film is anamorphous silicon film.
 40. A method of manufacturing anelectroluminescent display device, said method comprising the steps of;forming a first amorphous semiconductor film comprising silicon over afront surface and a back surface of a glass substrate having adistortion point of not lower than 750° C.: carrying out a first heattreatment to oxidize the first amorphous semiconductor film to form athermal oxidation film: forming a second amorphous semiconductor filmcomprising silicon over the thermal oxidation film formed over the frontsurface of the glass substrate; carrying out a second heat treatment tocrystallize the second amorphous semiconductor film to form acrystalline semiconductor film; and patterning the crystallinesemiconductor film to form an active layer.
 41. A method according toclaim 40, wherein the glass substrate is a crystallized glass substrate.42. A method according to claim 40, wherein the distortion point of theglass substrate is in a range of 950 to 1100° C.
 43. A method accordingto claim 40, wherein the crystalline semiconductor film is a siliconfilm.
 44. A method according to claim 40, wherein the first amorphoussemiconductor film is an amorphous silicon film.
 45. A method accordingto claim 40, wherein the first semiconductor film is formed over allsurfaces of the glass substrate.
 46. method according to claim 40,wherein the first semiconductor film is completely transformed into thethermal oxidation film by the first heat treatment.
 47. A methodaccording to claim 40, wherein the first semiconductor film is formedthrough a low pressure CVD method.
 48. A method according to claim 40,wherein the second semiconductor film further comprises germanium.
 49. Amethod according to claim 40, wherein the electroluminescent displaydevice is in combination with an electronic equipment, wherein theelectronic equipment is one selected from the group consisting of aportable telephone, a video camera, a mobile computer, a head mountdisplay, a rear type projector, a front type projector.
 50. A methodaccording to claim 40, wherein the second amorphous semiconductor filmis an amorphous silicon film.